Technical Field
[0001] The present invention relates to a compound containing a 1,3-diene structure and
a method for producing the same.
Background Art
[0002] A high molecular-weight light-emitting material and a charge transport material are
useful as e.g., a material for use in an organic layer of a light-emitting device
and thus have been studied in various ways. As the material above, for example, a
compound that can be hardened by crosslinking a benzocyclobutene residue for producing
a layered light-emitting device (Patent Literatures 1 and 2) and a compound having
two olefins (non-conjugated diene) useful for producing a layered light-emitting device
(Patent Literature 3) have been proposed.
Citation List
Patent Literature
Summary of Invention
Technical Problem
[0004] However, the aforementioned compound is insufficient in harden ability.
[0005] In the circumstances, an object of the present invention is to provide a compound
showing an excellent harden ability.
Solution to Problem
[0006] The present invention firstly provides a polymer compound having a polystyrene-equivalent
number average molecular weight of 1 × 10
3 to 1 × 10
8, having a conjugated main chain structure, and having a divalent group represented
by the following formula (I) as a repeating unit:
wherein Ar
1 is
- (a) a phenylene group or a fluorene-diyl group; or
- (b) a divalent group represented by the following formula (II):
wherein Y represents an oxygen atom, a sulfur atom, -N(R22)-, -O-C(R23)(R24)-, or -Si(R25)(R26)-; R22, R23, R24, R25 and R26 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an
aryl group or an arylalkyl group; and the formula may have a substituent; or
- (c) a divalent group represented by the following formula (III) or (IV):
wherein R3 represents a hydrogen atom, an alkyl group, an alkoxy group or a substituted amino
group; five R3 may be the same or different,
wherein R4 represents a hydrogen atom, an alkyl group, an alkoxy group or a substituted amino
group; and ten R4 may be the same or different; and wherein
J1 represents a phenylene group;
J2 represents an alkylene group;
X represents an oxygen atom or a sulfur atom;
j is 0 or 1, k is an integer of 0 to 3 and l is 0 or 1, such that 1 ≤ j + k + 1 ≤
5; m is 1 or 2;
R1 represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a halogen
atom, a cyano group or a nitro group;
a plurality of R1 may be the same or different; and
a plurality of J1, J2, X, j, k and l each may be the same or different.
[0007] The present invention secondly provides a composition comprising at least one selected
from the group consisting of a hole transport material, an electron transport material
and a light-emitting material, and the aforementioned compound.
[0008] The present invention thirdly provides a liquid composition containing the aforementioned
compound and a solvent.
[0009] The present invention fourthly provides a film containing the aforementioned compound
and a film formed by crosslinking the aforementioned compound.
[0010] The present invention fifthly provides a light-emitting device having electrodes
comprising an anode and a cathode and an organic layer provided between the electrodes
and containing the aforementioned compound.
[0011] The present invention sixthly provides a surface light source and a display having
the aforementioned light-emitting device.
[0012] The present invention seventhly provides an organic transistor and organic photoelectric
transducer formed by using the aforementioned compound.
[0013] The present invention eighthly provides a compound represented by the following formula
(X):
wherein Ar
1 is as defined herein ; J
1 represents a phenylene group, J
2 represents an alkylene group; X represents an oxygen atom or a sulfur atom; X
1 and X
2 each independently represent a bromine atom or an iodine atom; k is an integer of
0 to 3,1 is 0 or 1 and m is 1 or 2; and a plurality of J
1, J
2, X, k and l each may be the same or different.
[0014] The present invention ninthly provides a method for producing a compound represented
by the above formula (X), comprising reacting, in a base, a compound represented by
the following formula (XI):
wherein Ar
1 is as defined herein ; J
1 represents a phenylene group; X represents an oxygen atom or a sulfur atom; X
1 and X
2 each independently represent a bromine atom or an iodine atom; k is an integer of
0 to 3, 1 is 0 or 1 and m is 1 or 2; and a plurality of J
1, X, k and l each may be the same or different, and a compound represented by the
following formula (XII):
wherein X
3 represents a halogen atom; and J
2 represents an alkylene group.
Advantageous effects of Invention
[0015] The compound of the present invention is a compound showing an excellent harden ability
(for example, thermosetting property).
Description of Embodiments
[0016] The present invention will be more specifically described below. Note that, in the
specification, a diene structure such as a structure represented by the following
formula:
wherein R
1 is the same as defined above,
is expressed by E-form; however, a diene structure may be E-form, Z-form or a mixture
thereof
<Compound>
[0017] The compound of the present invention is a polymer compound having a divalent group
represented by the above formula (I) as a repeating unit. Furthermore, the compound
of the present invention, in view of harden ability, may have two or more types of
divalent groups represented by the above formula (I) as a repeating unit.
[0018] The compound of the present invention is a polymer compound. A polymer compound refers
to a compound having a polystyrene-equivalent number average molecular weight of 1
× 10
3 to 1 × 10
8. Furthermore, a polymer compound has a molecular-weight distribution.
[0019] In the above formula (I), Ar
1 is preferably an arylene group (a) in view of durability; in view of charge transport
property, a divalent heterocyclic group is preferred.
[0020] In the above formula (I), the arylene group (a) represented by Ar
1, is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon.
The arylene group (a) may have a substituent. Examples of the substituent include
an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group,
an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group,
an arylalkenyl group, an arylalkynyl group, an amino group, a substituted amino group,
a silyl group, a substituted silyl group, a halogen atom, an acyl group, an acyloxy
group, an imine residue, an amide group, an acid imide group, a monovalent heterocyclic
group, a carboxyl group, a substituted carboxyl group, a cyano group and a nitro group.
In view of solubility, fluorescence property, easiness of synthesis and characteristics
of the device to be obtained, etc. an alkyl group, an alkoxy group, an aryl group,
an aryloxy group, an arylalkyl group, an arylalkoxy group, a halogen atom or a cyano
group is preferable.
[0021] Examples of the arylene group represented by Ar
1 include a phenylene group (as shown in the following formulas 1 to 3), and a fluorene-diyl
group (as shown in the following formulas 36 to 38). Furthermore, as the arylene group
represented by Ar
1, in view of easiness of synthesizing the compound to be obtained, p-phenylene, m-phenylene
and 2,7-fluorene-diyl groups are more preferable, and p-phenylene and 2,7-fluorene-diyl
groups are particularly preferable. Note that the following groups may have a substituent.
[0022] The alkyl group serving as a substituent as mentioned above may be any one of linear,
branched and cyclic alkyl groups and may have a substituent. Such an alkyl group usually
has 1 to 20 carbon atoms. Examples thereof include a methyl group, an ethyl group,
a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group,
a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group,
a 2-ethylhexyl group, a nonyl group, a decyl group, a 3,7-dimethyloctyl group, a lauryl
group, a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group,
a perfluorohexyl group and a perfluorooctyl group.
[0023] The alkoxy group serving as a substituent as mentioned above may be any one of linear,
branched and cyclic alkoxy groups and may have a substituent. Such an alkoxy group
usually has 1 to 20 carbon atoms. Examples thereof include a methoxy group, an ethoxy
group, a propyloxy group, an isopropyloxy group, a butoxy group, an isobutoxy group,
a t-butoxy group, a pentyloxy group, a hexyloxy group, a cyclohexyloxy group, a heptyloxy
group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group,
a 3,7-dimethyloctyloxy group, a lauryloxy group, a trifluoromethoxy group, a pentafluoroethoxy
group, a perfluorobutoxy group, a perfluorohexyloxy group, a perfluorooctyloxy group,
a methoxymethyloxy group and a 2-methoxyethyloxy group.
[0024] The alkylthio group serving as a substituent as mentioned above may be any one of
linear, branched and cyclic alkylthio groups and may have a substituent. Such an alkylthio
group usually has about 1 to 20 carbon atoms. Specific examples thereof include a
methylthio group, an ethylthio group, a propylthio group, an isopropylthio group,
a butylthio group, an isobutylthio group, a t-butylthio group, a pentylthio group,
a hexylthio group, a cyclohexylthio group, a heptylthio group, an octylthio group,
a 2-ethylhexylthio group, a nonylthio group, a decylthio group, a 3,7-dimethyloctylthio
group, a laurylthio group and a trifluoromethylthio group.
[0025] The aryl group serving as a substituent as mentioned above is an atomic group, which
is obtained by removing a single hydrogen atom from an aromatic hydrocarbon, includes
an aryl group having a condensed ring, an aryl group to which an independent benzene
ring or two or more condensed rings are bonded directly or via a vinylene group or
the like. The aryl group usually has 6 to 60 carbon atoms and preferably 7 to 48 carbon
atoms. Examples thereof include a phenyl group, a C
1 to C
12 alkoxyphenyl group ("C
1 to C
12 alkoxy" means that the number of carbon atoms of the alkoxy moiety is 1 to 12. The
same is applied hereinafter), a C
1 to C
12 alkylphenyl group ("C
1 to C
12 alkyl" means that the number of carbon atoms of the alkyl moiety is 1 to 12. The
same is applied hereinafter), a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl
group, a 2-anthracenyl group, a 9-anthracenyl group and a pentafluorophenyl group;
and preferably a C
1 to C
12 alkoxyphenyl group and a C
1 to C
12 alkylphenyl group.
[0026] Examples of the C
1 to C
12 alkoxyphenyl group include a methoxyphenyl group, an ethoxyphenyl group, a propyloxyphenyl
group, an isopropyloxyphenyl group, a butoxyphenyl group, an isobutoxyphenyl group,
a t-butoxyphenyl group, a pentyloxyphenyl group, a hexyloxyphenyl group, a cyclohexyloxyphenyl
group, a heptyloxyphenyl group, an octyloxyphenyl group, a 2-ethylhexyloxyphenyl group,
a nonyloxyphenyl group, a decyloxyphenyl group, a 3,7-dimethyloctyloxyphenyl group
and a lauryloxyphenyl group.
[0027] Examples of the C
1 to C
12 alkylphenyl group include a methylphenyl group, an ethylphenyl group, a dimethylphenyl
group, a propylphenyl group, a mesityl group, a methylethylphenyl group, an isopropylphenyl
group, a butylphenyl group, an isobutylphenyl group, a t-butylphenyl group, a pentylphenyl
group, an isoamylphenyl group, a hexylphenyl group, a heptylphenyl group, an octylphenyl
group, a nonylphenyl group, a decylphenyl group and a dodecylphenyl group.
[0028] The aryloxy group serving as a substituent as mentioned above usually has 6 to 60
carbon atoms and preferably 7 to 48 carbon atoms. Examples of the aryloxy group include
a phenoxy group, a C
1 to C
12 alkoxyphenoxy group, a C
1 to C
12 alkylphenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group and a pentafluorophenyloxy
group; and preferably a C
1 to C
12 alkoxyphenoxy group and a C
1 to C
12 alkylphenoxy group.
[0029] Examples of the C
1 to C
12 alkoxyphenoxy group include a methoxyphenoxy group, an ethoxyphenoxy group, a propyloxyphenoxy
group, an isopropyloxyphenoxy group, a butoxyphenoxy group, an isobutoxyphenoxy group,
a t-butoxyphenoxy group, a pentyloxyphenoxy group, a hexyloxyphenoxy group, a cyclohexyloxyphenoxy
group, a heptyloxyphenoxy group, an octyloxyphenoxy group, a 2-ethylhexyloxyphenoxy
group, a nonyloxyphenoxy group, a decyloxyphenoxy group, a 3,7-dimethyloctyloxyphenoxy
group and a lauryloxyphenoxy group.
[0030] Examples of the C
1 to C
12 alkylphenoxy group include a methylphenoxy group, an ethylphenoxy group, a dimethylphenoxy
group, a propylphenoxy group, a 1,3,5-trimethylphenoxy group, a methylethylphenoxy
group, an isopropylphenoxy group, a butylphenoxy group, an isobutylphenoxy group,
a t-butylphenoxy group, a pentylphenoxy group, an isoamylphenoxy group, a hexylphenoxy
group, a heptylphenoxy group, an octylphenoxy group, a nonylphenoxy group, a decylphenoxy
group and a dodecylphenoxy group.
[0031] The arylthio group serving as a substituent as mentioned above may have a substituent
on the aromatic ring and usually has about 3 to 60 carbon atoms. Specific examples
thereof include a phenylthio group, a C
1 to C
12 alkoxyphenylthio group, a C
1 to C
12 alkylphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group and a pentafluorophenylthio
group.
[0032] The arylalkyl group serving as a substituent as mentioned above may have a substituent
and usually has about 7 to 60 carbon atoms. Specific examples thereof include a phenyl-C
1 to C
12 alkyl group, a C
1 to C
12 alkoxyphenyl-C
1 to C
12 alkyl group, a C
1 to C
12 alkylphenyl-C
1 to C
12 alkyl group, a 1-naphthyl-C
1 to C
12 alkyl group and a 2-naphthyl-C
1 to C
12 alkyl group.
[0033] The arylalkoxy group serving as a substituent as mentioned above may have a substituent
and usually has about 7 to 60 carbon atoms. Specific examples thereof include a phenyl-C
1 to C
12 alkoxy group, a C
1 to C
12 alkoxyphenyl-C
1 to C
12 alkoxy group, a C
1 to C
12 alkylphenyl-C
1 to C
12 alkoxy group, a 1-naphthyl-C
1 to C
12 alkoxy group and a 2-naphthyl-C
1 to C
12 alkoxy group.
[0034] The arylalkylthio group serving as a substituent as mentioned above may have a substituent
and usually has about 7 to 60 carbon atoms. Specific examples thereof include a phenyl-C
1 to C
12 alkylthio group, a C
1 to C
12 alkoxyphenyl-C
1 to C
12 alkylthio group, a C
1 to C
12 alkylphenyl-C
1 to C
12 alkylthio group, a 1-naphthyl-C
1 to C
12 alkylthio group and a 2-naphthyl-C
1 to C
12 alkylthio group.
[0035] The arylalkenyl group serving as a substituent as mentioned above usually has about
8 to 60 carbon atoms. Specific examples thereof include a phenyl-C
2 to C
12 alkenyl group, a C
1 to C
12 alkoxyphenyl-C
2 to C
12 alkenyl group, a C
1 to C
12 alkylphenyl-C
2 to C
12 alkenyl group, a 1-naphthyl-C
2 to C
12 alkenyl group and a 2-naphthyl-C
2 to C
12 alkenyl group. A C
1 to C
12 alkoxyphenyl-C
2 to C
12 alkenyl group and a C
1 to C
12 alkylphenyl-C
2 to C
12 alkenyl group are preferable.
[0036] The arylalkynyl group serving as a substituent as mentioned above usually has about
8 to 60 carbon atoms. Specific examples thereof include a phenyl-C
2 to C
12 alkynyl group, a C
1 to C
12 alkoxyphenyl-C
2 to C
12 alkynyl group, a C
1 to C
12 alkylphenyl-C
2 to C
12 alkynyl group, a 1-naphthyl-C
2 to C
12 alkynyl group and a 2-naphthyl-C
2 to C
12 alkynyl group. AC
1 to C
12 alkoxyphenyl-C
2 to C
12 alkynyl group and a C
1 to C
12 alkylphenyl-C
2 to C
12 alkynyl group are preferable.
[0037] The substituted amino group serving as a substituent as mentioned above may be an
amino group substituted with one or two groups selected from an alkyl group, an aryl
group, an arylalkyl group and a monovalent heterocyclic group. The alkyl group, aryl
group, arylalkyl group or monovalent heterocyclic group may have a substituent. The
number of carbon atoms of the substituted amino group excluding the number of carbon
atoms of a substituent is usually about 1 to 60 and preferably 2 to 48 carbon atoms.
[0038] Specific examples thereof include a methylamino group, a dimethylamino group, an
ethylamino group, a diethylamino group, a propylamino group, a dipropylamino group,
an isopropylamino group, a diisopropylamino group, a butylamino group, an s-butylamino
group, an isobutylamino group, a t-butylamino group, a pentylamino group, a hexylamino
group, a cyclohexylamino group, a heptylamino group, an octylamino group, a 2-ethylhexylamino
group, a nonylamino group, a decylamino group, a 3,7-dimethyloctylamino group, a laurylamino
group, a cyclopentylamino group, a dicyclopentylamino group, a dicyclohexylamino group,
a pyrrolidyl group, a piperidyl group, a ditrifluoromethylamino group, a phenylamino
group, a diphenylamino group, a C
1 to C
12 alkoxyphenylamino group, a di(C
1 to C
12 alkoxyphenyl)amino group, a di(C
1 to C
12 alkylphenyl)amino group, a 1-naphthylamino group, a 2-naphthylamino group, a pentafluorophenylamino
group, a pyridylamino group, a pyridazinylamino group, a pyrimidylamino group, a pyrazylamino
group, a triazylamino group, a phenyl-C
1 to C
12 alkylamino group, a C
1 to C
12 alkoxyphenyl-C
1 to C
12 alkylamino group, a C
1 to C
12 alkylphenyl-C
1 to C
12 alkylamino group, a di(C
1 to C
12 alkoxyphenyl-C
1 to C
12 alkyl)amino group, a di(C
1 to C
12 alkylphenyl-C
1 to C
12 alkyl)amino group, a 1-naphthyl-C
1 to C
12 alkylamino group and a 2-naphthyl-C
1 to C
12 alkylamino group.
[0039] The substituted silyl group serving as a substituent as mentioned above may be a
silyl group substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl
group, an arylalkyl group and a monovalent heterocyclic group. The number of carbon
atoms of the substituted silyl group is usually about 1 to 60 and preferably 3 to
48. Note that the alkyl group, aryl group, arylalkyl group or monovalent heterocyclic
group may have a substituent.
[0040] Specific examples thereof include a trimethylsilyl group, a triethylsilyl group,
a tripropylsilyl group, a tri-isopropylsilyl group, a dimethyl-isopropylsilyl group,
a diethyl-isopropylsilyl group, a t-butyldimethylsilyl group, a pentyldimethylsilyl
group, a hexyldimethylsilyl group, a heptyldimethylsilyl group, an octyldimethylsilyl
group, a 2-ethylhexyl-dimethylsilyl group, a nonyldimethylsilyl group, a decyldimethylsilyl
group, a 3,7-dimethyloctyl-dimethylsilyl group, a lauryldimethylsilyl group, a phenyl-C
1 to C
12 akylsilyl group, a C
1 to C
12 alkoxyphenyl-C
1 to C
12 alkylsilyl group, a C
1 to C
12 alkylphenyl-C
1 to C
12 alkylsilyl group, a 1-naphthyl-C
1 to C
12 alkylsilyl group, a 2-naphthyl-C
1 to C
12 alkylsilyl group, a phenyl-C
1 to C
12 alkyldimethylsilyl group, a triphenylsilyl group, a tri-p-xylylsilyl group, a tribenzylsilyl
group, a diphenylmethylsilyl group, a t-butyldiphenylsilyl group and a dimethylphenylsilyl
group.
[0041] Examples of a halogen atom serving as a substituent as mentioned above include a
fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
[0042] The acyl group serving as a substituent as mentioned above usually has about 2 to
20 carbon atoms and preferably 2 to 18 carbon atoms. Specific examples thereof include
an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl
group, a benzoyl group, a trifluoroacetyl group and a pentafluorobenzoyl group.
[0043] The acyloxy group serving as a substituent as mentioned above usually has about 2
to 20 carbon atoms and preferably 2 to 18 carbon atoms. Specific examples thereof
include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy
group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetyloxy group and a pentafluorobenzoyloxy
group.
[0045] The carbamoyl group serving as a substituent as mentioned above usually has about
2 to 20 carbon atoms and preferably 2 to 18 carbon atoms. Specific examples thereof
include a formamide group, an acetamide group, a propioamide group, a butyroamide
group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group,
a diformamide group, a diacetamide group, a dipropioamide group, a dibutyroamide group,
a dibenzamide group, a ditrifluoroacetamide group and a dipentafluorobenzamide group.
[0047] The monovalent heterocyclic group serving as a substituent as mentioned above refers
to a remaining atomic group obtained by removing a single hydrogen atom from a heterocyclic
compound and usually having about 4 to 60 carbon atoms and preferably 4 to 20 carbon
atoms. Of the monovalent heterocyclic groups, a monovalent aromatic heterocyclic group
is preferable. Note that the number of carbon atoms of a substituent is not included
in the number of carbon atoms of a heterocyclic group. The heterocyclic compound herein
refers to an organic compound having a ring structure, which is not only constituted
of a carbon atom but also contains a hetero atom such as oxygen, sulfur, nitrogen,
phosphorus and boron, within the ring. Specific examples thereof include a thienyl
group, a C
1 to C
12 alkylthienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a C
1 to C
12 alkylpyridyl group, a piperidyl group, a quinolyl group and an isoquinolyl group.
A thienyl group, a C
1 to C
12 alkyl thienyl group, a pyridyl group and a C
1 to C
12 alkyl pyridyl group are preferable.
[0048] Examples of the substituted carboxyl group serving as a substituent as mentioned
above refers to a carboxyl group substituted with an alkyl group, an aryl group, an
arylalkyl group or a monovalent heterocyclic group and usually having about 2 to 60
carbon atoms and preferably 2 to 48 carbon atoms. Specific examples thereof include
a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl
group, a butoxycarbonyl group, an isobutoxycarbonyl group, a t-butoxycarbonyl group,
a pentyloxycarbonyl group, a hexyloxycarbonyl group, a cyclohexyloxycarbonyl group,
a heptyloxycarbonyl group, an octyloxycarbonyl group, a 2-ethylhexyloxycarbonyl group,
a nonyloxycarbonyl group, a decyloxycarbonyl group, a 3,7-dimethyloctyloxycarbonyl
group, a dodecyloxycarbonyl group, a trifluoromethoxycarbonyl group, a pentafluoroethoxycarbonyl
group, a perfluorobutoxycarbonyl group, a perfluorohexyloxycarbonyl group, a perfluorooctyloxycarbonyl
group, a phenoxycarbonyl group, a naphthoxycarbonyl group and a pyridyloxycarbonyl
group. Note that the alkyl group, aryl group, arylalkyl group or monovalent heterocyclic
group may have a substituent. The number of carbon atoms of the substituent is not
included in the number of carbon atoms of the substituted carboxyl group.
[0049] In the above formula (I), the divalent heterocyclic group (b) represented by Ar
1 refers to the remaining atomic group obtained by removing two hydrogen atoms from
a heterocyclic compound. The divalent heterocyclic group (b) may have a substituent.
[0050] As the substituent, in view of solubility of, fluorescence property of, easiness
of synthesizing the compound to be obtained and characteristic of the device to be
obtained, etc., an alkyl group, an alkoxy group, an aryl group, an aryloxy group,
an arylalkyl group, an arylalkoxy group, a halogen atom or cyano group is preferable.
These groups and atoms are defined as described above.
[0051] Examples of the divalent heterocyclic group (b) represented by Ar
1 include the following groups. Note that the following groups may have a substituent.
[0052] A group containing an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom,
etc. as a hetero atom and having a fluorene structure (as shown in the following formulas
129 to 136).
[0054] The divalent heterocyclic group (b) represented by Ar
1 is a divalent group represented by the following formula (II):
wherein Y represents an oxygen atom, a sulfur atom, -N(R
22)-, -O-C(R
23)(R
24)-, or -Si(R
25)(R
26)-; R
22, R
23, R
24, R
25 and R
26 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an
aryl group or an arylalkyl group; and the formula may have a substituent.
[0055] When the above formula (II) has a substituent, examples of the substituent include
an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group
and an arylalkoxy group. These groups are the same as defined above.
[0056] In the above formula (II), in view of easiness of synthesizing the compound of the
present invention, Y is preferably an oxygen atom, a sulfur atom and -N(R
22)- and more preferably an oxygen atom and -N(R
22)-.
[0057] A divalent group represented by the above formula (II) is preferably a divalent group
represented by the following formula (II)-1 or the following formula (II)-2, since
a particularly high charge transport property can be obtained.
wherein Y
1 represents an oxygen atom, a sulfur atom, -N(R
22)-, -O-C(R
23)(R
24)-, or -Si(R
25)(R
26)-; and the formula may have a substituent.
wherein Y
2 represents an oxygen atom, a sulfur atom, -N(R
22)-, -O-C(R
23)(R
24)- or -Si(R
25)(R
26)-; and the formula may have a substituent.
[0058] When the above formulas (II)-1 and (II)-2 have a substituent, examples of the substituent
include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl
group and an arylalkoxy group. These groups are the same as defined above.
[0059] In the above formula (II)-1, in view of easiness of synthesizing the compound of
the present invention, Y
1 is preferably an oxygen atom, a sulfur atom, or -N(R
22)-, more preferably an oxygen atom or -N(R
22)- and particularly preferably an oxygen atom.
[0060] In the above formula (II)-2, in view of easiness of synthesizing the compound of
the present invention, Y
2 is preferably an oxygen atom, a sulfur atom or -N(R
22)-,more preferably a sulfur atom or -N(R
22)- and particularly preferably -N(R
22)-.
[0061] The divalent aromatic amine group (c) represented by Ar
1 refers to the remaining atomic group obtained by removing two hydrogen atoms from
an aromatic amine.
[0062] The divalent aromatic amine (c) group may have a substituent. The substituent is,
in view of solubility of, fluorescence property of and easiness of synthesizing the
compound to be obtained, and easiness of crosslinking a film, preferably an alkyl
group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy
group, a halogen atom and cyano group. These groups and atoms are the same as defined
above.
[0063] Examples of the divalent aromatic amine group (c) represented by Ar
1 include divalent groups represented by the following formulas 201 to 202. Note that
the following groups may have a substituent.
[0064] The divalent aromatic amine group represented by Ar
1 is a divalent group represented by the following formula (III):
wherein R
3 represents a hydrogen atom, an alkyl group, an alkoxy group or a substituted amino
group; and five R
3 may be the same or different,
or a divalent group represented by the following formula (IV):
wherein R
4 represents a hydrogen atom, an alkyl group, an alkoxy group or a substituted amino
group; and ten R
4 may be the same or different.
[0065] In the above formulas (III) and (IV), the alkyl group and alkoxy group represented
by R
3 and R
4 are the same as defined above.
[0066] In the above formulas (III) and (IV), as the substituted amino group represented
by R
3 and R
4, an amino group substituted with one or two groups selected from an alkyl group,
an aryl group, an arylalkyl group and a monovalent heterocyclic group. The alkyl group,
aryl group, arylalkyl group and monovalent heterocyclic group may have a substituent.
The number of carbon atoms of the substituted amino group excluding the number of
carbon atoms of the substituent is usually 1 to 60 and preferably 2 to 48.
[0067] The substituted amino groups represented by R
3 and R
4 are the same as defined above.
[0068] In the above formula (I), the phenylene group represented by J
1 may have a substituent. Examples of the phenylene group include an o-phenylene, m-phenylene
and p-phenylene. Examples of the substituent include an alkyl group, an alkoxy group,
a halogen atom and a cyano group. These groups are the same as defined above.
[0069] In the above formula (I), the alkylene group represented by J
2 may be a linear or branched group. Examples of the alkyllene group include methylene,
1,2-ethylene, 1,3-propylene, 1,3-butylene, 1,4-butylene, 1,3-pentylene, 1,4-pentylene,
1,5-pentylene, 1,4-hexylene, 1,6-hexylene, 1,7-heptylene, 1,6-octylene and 1,8-octylene.
[0070] In the above formula (I), X is, in view of easiness of synthesizing the compound
of the present invention, preferably an oxygen atom.
[0071] In the above formula (I), in view of easiness of synthesizing the compound, j is
0 or 1 and particularly preferably 1, of the present invention.
[0072] In the above formula (I), in view of easiness of synthesizing the compound of the
present invention, k is preferably an integer selected from 0 to 2 and further preferably
0 or 1.
[0073] In the above formula (I), the alkyl group, alkoxy group, aryl group, halogen atom,
cyano group and nitro group represented by R
1 are the same as defined above. However, in view of harden ability, a hydrogen atom,
an alkyl group, an alkoxy group, a halogen atom, a nitro group and a cyano group are
preferable; a hydrogen atom, an alkyl group, an aryl group and a halogen atom are
more preferable; a hydrogen atom and an alkyl group are further preferable; and a
hydrogen atom is particularly preferable.
[0074] In the above formula (I), a group represented by the following formula (Ia):
wherein j, k, l, J
1, J
2 and R
1 are the same as defined above,
is, in view of harden ability of the compound of the present invention, preferably
a group represented by the following formula (Ib):
wherein k, l, J
2 and R
1 are the same as defined above,
and more preferably a group represented by the following formula (Ic):
wherein k, l and J
2 are the same as defined above,
and a group represented by the following formula (Id):
wherein k, l and J
2 are the same as defined above.
[0076] In view of easiness of synthesizing the polymer compound, the compound of the present
invention is preferably a polymer compound having, as the group represented by the
above formula (I), a repeating unit represented by the following formula (V):
wherein J
1, J
2, X, R
1, k, l and m are the same as defined above; and R
2 represents an alkyl group,
an aryl group, an arylalkyl group or an arylalkoxy group.
[0077] In the above formula (V), the alkyl group, aryl group, arylalkyl group and arylalkoxy
group represented by R
2 are the same as defined above.
[0078] In view of harden ability of the polymer compound, the compound of the present invention
may further have a repeating unit containing a crosslinking group.
[0079] The crosslinking group refers to a substituent inducing a crosslinking reaction by
stimulation of heat or light.
[0080] Examples of the crosslinking group include an oxiranyl group, an oxetanyl group,
a cinnamoyl group, a dienophile group and an alkynyl group.
[0081] In view of harden ability, the polymer compound preferably has, in addition to a
repeating unit represented by the above formula (I), a repeating unit represented
by the following formula (A):
wherein Ar
2 represents an arylene group, a divalent heterocyclic group or a divalent aromatic
amine group; J
3 represents a direct bond, an alkylene group or a phenylene group; and n represents
1 or 2; and a plurality of J
3 may be the same or different.
[0082] In the above formula (A), the arylene group, divalent heterocyclic group and divalent
aromatic amine group represented by Ar
2 are the same as defined above. As Ar
2, in view of easiness of synthesizing the compound of the present invention, an arylene
group and a divalent heterocyclic group are preferable, an arylene group is more preferable,
a fluorene-diyl group is further preferable and a 2,7-fluorene-diyl group is particularly
preferable.
[0083] In the above formula (A), the alkylene group and phenylene group represented by
J
3 are the same as defined above.
[0084] In the group represented by the above formula (A), it is particularly preferable
that Ar
2 is an arylene group, J
3 is a direct bond and n is 2.
[0085] The polymer compound preferably contains, in view of harden ability, in addition
to the repeating unit represented by the above formula (I), a repeating unit represented
by the following formula (B):
wherein Ar
3 represents an arylene group, a divalent heterocyclic group or a divalent aromatic
amine group; J
4 represents a direct bond, an alkylene group or a phenylene group; R
5 represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group,
an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy
group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino
group, a substituted amino group, a silyl group, a substituted silyl group, a halogen
atom, an acyl group, an acyloxy group, an imine residue, a carbamoyl group, an acid
imide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl
group, a cyano group or a nitro group; o represents 1 or 2; a plurality of R
5 may be the same or different; and a plurality of J
4 may be the same or different.
[0086] In the above formula (B), the arylene group, divalent heterocyclic group and divalent
aromatic amine group represented by Ar
3 may be the same as defined above. As Ar
3, in view of easiness of synthesizing the compound of the present invention, an arylene
group and a divalent heterocyclic group are preferable, an arylene group is more preferable,
a fluorene-diyl group is further preferable and 2,7-fluorene-diyl group is particularly
preferable.
[0087] In the above formula (B), the alkylene group and phenylene group represented by J
4 are the same as defined above.
[0088] In the above formula (B), the alkyl group, alkoxy group, alkylthio group, aryl group,
aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group,
arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl
group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue,
carbamoyl group, acid imide group, monovalent heterocyclic group, carboxyl group,
substituted carboxyl group, cyano group or nitro group represented by R
5 is the same as defined above. As R
5, in view of harden ability of the compound of the present invention, a hydrogen atom
and a halogen atom are preferable and a hydrogen atom is more preferable.
[0089] In the group represented by the above formula (B), it is particularly preferable
that Ar
3 is an arylene group, J
4 is an alkylene group and o is 2.
[0090] In view of charge transport property of the polymer compound, the compound of the
present invention further preferably contains, in addition to the repeating unit represented
by the above formula (I), a repeating unit represented by the following formula (C):
wherein R
6 represents an alkyl group, an aryl group, an arylalkyl group or an arylalkoxy group;
and two R
6 may be the same or different.
[0091] In the above formula (C), the alkyl group, aryl group, arylalkyl group and arylalkoxy
group represented by R
6 are the same as defined above. As R
6, in view of easiness of synthesizing a raw-material monomer, an alkyl group or an
aryl group is preferable and an alkyl group is further preferable.
[0092] The polymer compound may have, in view of hole transport property, in addition to
the repeating unit represented by the above formula (I), one or more repeating unit
selected from the group consisting of repeating units represented by the following
formula (D) and repeating units represented by the following formula (E).
wherein Ar
3, Ar
4, Ar
5 and Ar
6 each independently represent an arylene group or a divalent heterocyclic group; Ar
7, Ar
8 and Ar
9 each independently represent an aryl group or a monovalent heterocyclic group; α
and β each independently represent 0 or 1; and Ar
3, Ar
4, Ar
5, Ar
6, Ar
7, Ar
8 and Ar
9 may have a substituent.
wherein ring P and ring Q each independently represent an aromatic hydrocarbon ring;
X
3 represents a single bond, an oxygen atom and a sulfur atom; and R
100 represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an
aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio
group, an arylalkenyl group, an arylalkynyl group, an amino group, a substituted amino
group, a silyl group, a substituted silyl group, a halogen atom, an acyl group, an
acyloxy group, an imine residue, a carbamoyl group, an acid imide group, a monovalent
heterocyclic group, a carboxyl group, a substituted carboxyl group, a cyano group
or a nitro group.
[0093] In the above formula (D), the arylene group, divalent heterocyclic group, aryl group
and monovalent heterocyclic group are the same as defined above.
[0094] Examples of the substituent that Ar
3, Ar
4, Ar
5, Ar
6, Ar
7, Ar
8 and Ar
9 may have include an alkyl group, an alkoxy group, an alkylthio group, an aryl group,
an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio
group, an arylalkenyl group, an arylalkynyl group, an amino group, a substituted amino
group, a silyl group, a substituted silyl group, a halogen atom, an acyl group, an
acyloxy group, an imine residue, a carbamoyl group, an acid imide group, a monovalent
heterocyclic group, a carboxyl group, a substituted carboxyl group, a cyano group
and a nitro group.
[0095] The alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio
group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group,
arylalkynyl group, amino group, substituted amino group, silyl group, substituted
silyl group, halogen atom, acyl group, acyloxy group, imine residue, carbamoyl group,
acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl
group, cyano group and nitro group are the same as defined above.
[0096] In the above formula (E), the aromatic hydrocarbon ring represents an aromatic hydrocarbon
ring obtained by removing two bonds from an arylene group as mentioned above.
[0097] In the above formula (E), the alkyl group, alkoxy group, alkylthio group, aryl group,
aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group,
arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl
group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue,
carbamoyl group, acid imide group, monovalent heterocyclic group, carboxyl group,
substituted carboxyl group, cyano group and nitro group are the same as defined above.
[0098] The repeating unit represented by the above formula (D) is, in view of hole transport
property, preferably a repeating unit represented by the following formula (D)-1 or
(D)-2.
wherein R
7 represents a hydrogen atom, an alkyl group or an alkoxy group; and three R
7 may be the same or different.
wherein R
8 represents a hydrogen atom, an alkyl group or an alkoxy group; and six R
8 may be the same or different.
[0099] In the above formula (B)-1, the alkyl group and alkoxy group represented by R
7 are the same as defined above.
[0100] In the above formula (B)-2, the alkyl group and alkoxy group represented by R
8 are the same as defined above.
[0101] The repeating unit represented by the above formula (E) is, in view of hole transport
property, preferably a repeating unit represented by the following formula (E)-1.
wherein R
9 is an alkyl group, an aryl group, an arylalkyl group or an arylalkoxy group.
[0102] In the above formula (E)-1, the alkyl group, aryl group, arylalkyl group and arylalkoxy
group represented by R
7 are the same as defined above.
[0103] In view of charge transport property of the polymer compound, the compound of the
present invention may have, in addition to the repeating unit represented by the above
formula (I), one or more of the repeating units represented by the following formulas
(G), (H), (J) and (K).
wherein R
10 represents an alkyl group, an aryl group, an arylalkyl group or an arylalkoxy group;
and two R
10 may be the same or different.
wherein R
11 represents an alkyl group, an alkoxy group, an aryl group, an arylalkyl group or
an arylalkoxy group; q represents an integer selected from 0 to 4; and a plurality
of R
11 may be the same or different.
wherein R
12 represents an alkyl group, an alkoxy group, an aryl group, an arylalkyl group or
an arylalkoxy group; Z represents an oxygen atom or a sulfur atom; r is an integer
of 0 to 3; and a plurality of R
12 may be the same or different.
wherein R
13 represents an alkyl group, an alkoxy group, an aryl group, an arylalkyl group or
an arylalkoxy group; s is an integer of 0 to 2; and a plurality of R
13 may be the same or different.
[0104] In the above formula (G), the alkyl group, aryl group, arylalkyl group and arylalkoxy
group represented by R
10 are the same as defined above.
[0105] . In the above formula (H), the alkyl group, alkoxy group, aryl group, arylalkyl
group and arylalkoxy group represented by R
11 are the same as defined above.
[0106] In the above formula (J), the alkyl group, alkoxy group, aryl group, arylalkyl group
and arylalkoxy group represented by R
12 are the same as defined above.
[0107] In the above formula (K), the alkyl group, alkoxy group, aryl group, arylalkyl group
and arylalkoxy group represented by R
13 are the same as defined above.
[0108] In view of luminous efficiency of the resultant compound preferably has a repeating
unit represented by the above formula (I), the repeating unit represented by the above
formula (C) and the repeating units represented by the above formulas (D) and (E).
[0109] In view of harden ability, the compound of the present invention preferably has a
repeating unit represented by the above formulas (D) and (E).
[0110] In the compound of the present invention, the uppermost ratio (molar ratio) of the
repeating unit represented by the above formula (I) is usually, in view of stability
of the compound, 1 relative to the total repeating units, preferably 0.5, more preferably
0.3, and most preferably 0.15. The lowermost ratio (molar ratio) is, in view of harden
ability of the compound, usually 0.01, preferably 0.02, more preferably 0.05 and most
preferably 0.10.
[0111] Furthermore, when the compound of the present invention is a polymer compound having
the repeating unit represented by the above formula (I), the repeating unit represented
by the above formula (C) and the repeating units represented by the above formulas
(D) and (E), the molar ratio of the repeating unit represented by the above formula
(C) is usually, 0.1 to 0.95 relative to the total repeating units and preferably 0.3
to 0.9, whereas the whole molar ratio of the repeating units represented by the above
formulas (D) and (E) is usually 0.01 to 0.5 and preferably 0.05 to 0.3.
[0112] The compound of the present invention, in view of the life property of the light-emitting
device that is formed by using the compound, preferably has a polystyrene-equivalent
number average molecular weight of 1 × 10
3 to 1 × 10
8, preferably 1 × 10
3 to 1 × 10
7, further preferably 1 × 10
4 to 1 × 10
7 and particularly preferably 5 × 10
4 to 1 × 10
7.
[0113] The compound of the present invention, in view of harden ability, has a polystyrene-equivalent
weight average molecular weight of 1 × 10
3 to 1 × 10
8, preferably 1 × 10
4 to 1 × 10
7 and particularly preferably 1 × 10
5 to 1 × 10
7.
[0114] In the specification, a number average molecular weight and a weight average molecular
weight were obtained by size exclusion chromatography (SEC) (trade name: LC-10Avp
manufactured by Shimadzu Corporation) as a polystyrene-equivalent number average molecular
weight and weight average molecular weight. Of the methods of SEC, chromatography
using an organic solvent as a mobile phase is referred to as gel permeation chromatography
(GPC). The polymer to be measured was dissolved in tetrahydrofuran at a concentration
of about 0.5 wt% and 30 µL of the solution was loaded in GPC. As the mobile phase
of GPC, tetrahydrofuran was used and allowed to flow at a rate of 0.6 mL/minute. As
the column, two TSKgel SuperHM-H (manufactured by Tosoh Corporation) columns and a
single TSKgel SuperH2000 (manufactured by Tosoh Corporation) column were connected
in series. As the detector, a differential refractive index detector (trade name:
RID-10A, manufactured by Shimadzu Corporation) was used. Measurement was performed
at 40°C.
[0115] The compound of the present invention may be any one of an alternating copolymer,
a random copolymer, a block copolymer and a graft copolymer, or may be a polymer compound
having an intermediate structure of them, for example, a random copolymer partially
having a block copolymer. The compound of the present invention is, in view of fluorescence
or phosphorescence quantum yield, preferably a random copolymer partially having a
block copolymer, a block copolymer and a graft copolymer rather than a complete random
copolymer. In the compound of the present invention, a dendrimer having a branch in
the main chain and three or more terminal portions is included.
[0116] If a polymerizable group remains as it is as a terminal group of the compound of
the present invention, the luminescence property and life of the light-emitting device
produced by using the compound may sometimes decrease. Because of this, the terminal
group may be protected with a stable group. As the terminal group, a group having
a conjugated bond continued to a conjugated structure of the main chain is preferable.
For example, a group connected to an aryl group or a monovalent heterocyclic group
via a carbon-carbon bond is mentioned. Alternatively, a substituent and the like described
in
JP 9-45478 A, Formula 10, may be mentioned.
[0118] Next, a method for producing the compound of the present invention will be described.
[0119] The compound may be manufactured in any method, for example, by condensation polymerization
of a compound represented by the formula: Z
1-A
1-Z
2. Note that in the above formula, A
1 represents a repeating unit represented by the above formula (I). Furthermore, in
the above formula, Z
1 and Z
2 each independently represent a polymerizable group.
[0120] Furthermore, when the compound of the present invention is a polymer compound having
a repeating unit represented by the above formula (A) to (H), (J) or (K), the compound
of the present invention can be produced by condensation polymerization of a compound
represented by the formula: Z
3-A
2-Z
4 corresponding to the repeating unit. Furthermore, in the above formula, Z
3 and Z
4 each independently represent a polymerizable group.
[0121] Examples of the polymerizable group include a halogen atom, an alkylsulfonate group,
an arylsulfonate group, an arylalkylsulfonate group, a boric acid ester residue, a
sulfoniummethyl group, a phosphoniummethyl group, a phosphonatemethyl group, a monohalogenated
methyl group, a boric acid residue (-B(OH)
2), a formyl group, a cyano group and a vinyl group.
[0122] Examples of the halogen atom serving as a polymerizable group include a fluorine
atom, a chlorine atom, a bromine atom and an iodine atom.
[0123] Examples of the alkylsulfonate group serving as a polymerizable group include a methanesulfonate
group, an ethanesulfonate group and a trifluoromethanesulfonate group.
[0124] Examples of the arylsulfonate group serving as a polymerizable group include a benzenesulfonate
group and a p-toluenesulfonate group.
[0125] Examples of the arylalkylsulfonate group serving as a polymerizable group include
a benzylsulfonate group.
[0126] Examples of the boric acid ester residue serving as a polymerizable group include
groups represented by the following formulas:
wherein Me represents a methyl group and Et represents an ethyl group.
[0127] Examples of the sulfoniummethyl group serving as a polymerizable group include groups
represented by the following formulas:
-CH
2S
+Me
2X'
-, -CH
2S
+Ph
2X'
-
wherein X' represents a halogen atom and Ph represents a phenyl group.
[0128] Examples of the phosphoniummethyl group serving as a polymerizable group include
groups represented by the following formula:
-CH
2P
+Ph
3X'
-
wherein X' represents a halogen atom.
[0129] Examples of the phosphonatemethyl group serving as a polymerizable group include
groups represented by the following formula:
-CH
2PO(OR')
2
wherein R' represents an alkyl group, an aryl group or an arylalkyl group.
[0130] Examples of the monohalogenated methyl group serving as a polymerizable group include
a methyl fluoride group, a methyl chloride group, a methyl bromide group and a methyl
iodide group.
[0131] When a zero-valence nickel complex for the Yamamoto coupling reaction or the like
is used, examples of the polymerizable group include a halogen atom, an alkylsulfonate
group, an arylsulfonate group and an arylalkylsulfonate group. When a nickel catalyst
or a palladium catalyst for the Suzuki coupling reaction or the like is used, examples
thereof include an alkylsulfonate group, a halogen atom, a boric acid ester residue
and boric acid residue.
[0132] The compound of the present invention is produced by using a compound having a plurality
of polymerizable groups serving as a monomer, if necessary, dissolved in an organic
solvent, and using, for example, an alkali and an appropriate catalyst and at a temperature
of not less than the melting point of the organic solvent and not more than the boiling
point. Examples of the method that can be used include methods described in "
Organic Reactions", Vol. 14, pages 270-490, John Wiley & Sons, Inc., 1965, "
Organic Syntheses", Collective Volume VI, pages 407-411, John Wiley & Sons, Inc.,
1988,
Chem. Rev., Vol. 95, page 2457 (1995),
J. Organomet. Chem., Vol. 576, page 147 (1999),
Makromol. Chem., Macromol. Symp.), Vol. 12, page 229 (1987).
[0133] In the method for producing the compound of the present invention, a known condensation
reaction can be used depending upon the type of polymerizable group. Examples thereof
include a method of polymerizing the corresponding monomer by the Suzuki coupling
reaction, a method of polymerizing by the Grignard reaction, a method of polymerizing
by an Ni(0) complex, a method of polymerizing by an oxidizing agent such as FeCl
3, a method of performing oxidative polymerization in an electrochemical manner and
a method by decomposing an intermediate polymer having an appropriate leaving group.
[0134] Of these, a method of polymerizing by the Suzuki coupling reaction, a method of polymerizing
by the Grignard reaction, and a method of polymerizing by a nickel zero-valence complex
are preferable in view of structural control.
[0135] Of the methods for producing the compound of the present invention, a production
method using a polymerizable group selected from a halogen atom, an alkylsulfonate
group, an arylsulfonate group and an arylalkylsulfonate group through and performed
by a condensation polymerization in the presence of a nickel zero-valence complex
is preferable.
[0136] Examples of a compound serving as a raw material for the compound of the present
invention include a dihalogenated compound, a bis(alkylsulfonate) compound, a bis(arylsulfonate)
compound, a bis(arylalkyl sulfonate) compound, a halogen-alkylsulfonate compound,
a halogen-arylsulfonate compound, a halogen-arylalkylsulfonate compound, an alkylsulfonate-arylsulfonate
compound, an alkylsulfonate-arylalkylsulfonate compound and an arylsulfonate-arylalkylsulfonate
compound. Furthermore, when a polymer compound controlled in sequence is produced,
examples of the compound that may be preferably used include a halogen-alkylsulfonate
compound, a halogen-arylsulfonate compound, a halogen-arylalkylsulfonate compound,
an alkylsulfonate-arylsulfonate compound, an alkylsulfonate-arylalkylsulfonate compound
and an arylsulfonate-arylalkylsulfonate compound.
[0137] A method for producing the compound of the present invention is, in view of easiness
of synthesizing the polymer compound, preferably a production method using a polymerizable
group, which is selected from a halogen atom, an alkylsulfonate group, an arylsulfonate
group, an arylalkylsulfonate group, a boric acid residue and a boric acid ester residue
such that the ratio of the total mole number (J) of the halogen atom, alkylsulfonate
group, arylsulfonate group and arylalkylsulfonate group contained in the whole raw-material
compound and the total mole number (K) of boric acid residue and boric acid ester
residue becomes substantially 1 (usually, K/J is 0.7 to 1.2), and performed by a condensation
polymerization method using a nickel catalyst or a palladium catalyst.
[0138] Examples of a combination of compounds serving as raw materials (more specifically,
a compound represented by the above formula: Y
1-A
1-Y
2 and a compound represented by the above formula: Y
3-A
2-Y
4) include a combination of a dihalogenated compound, a bis(alkylsulfonate) compound,
a bis(arylsulfonate) compound or a bis(arylalkylsulfonate) compound and a diboric
acid compound or diboric acid ester compound.
[0139] Furthermore, when a polymer compound controlled in sequence is produced, examples
of the compound that may be preferably used include a halogen-boric acid compound,
a halogen-boric acid ester compound, an alkylsulfonate-boric acid compound, an alkylsulfonate-boric
acid ester compound, an arylsulfonate-boric acid compound, an arylsulfonate-boric
acid ester compound, an arylalkylsulfonate-boric acid compound, an arylalkylsulfonate-boric
acid compound and an arylalkylsulfonate-boric acid ester compound.
[0140] The organic solvent to be used in the condensation polymerization is preferably treated
in advance sufficiently in a deoxidization process and a dehydration process in order
to suppress a side reaction. However, this is not applied to the case where a reaction
is performed in a two-phase system with water like the Suzuki coupling reaction.
[0141] Examples of the organic solvent to be used in the condensation polymerization include
saturated hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane; unsaturated
hydrocarbons such as benzene, toluene, ethylbenzene and xylene; halogenated saturated
hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, chlorobutane,
bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane
and bromocyclohexane; halogenated unsaturated hydrocarbon such as chlorobenzene, dichlorobenzene
and trichlorobenzene; alcohols such as methanol, ethanol, propanol, isopropanol, butanol
and t-butyl alcohol; carboxylic acids such as formic acid, acetic acid and propionic
acid; ethers such as dimethyl ether, diethyl ether, methyl-t-butyl ether, tetrahydrofuran,
tetrahydropyrane and dioxane; amines such as trimethylamine, triethylamine, N,N,N',N'-tetramethylethylenediamine
and pyridine; and amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide
and N-methylmorpholineoxide. Ethers are preferable and tetrahydrofuran and diethylether
are particularly preferable. These organic solvents may be used alone or in combination
with two or more types.
[0142] In the condensation polymerization, an alkali and a suitable catalyst may be appropriately
added to facilitate the reaction. The alkali and catalyst are preferably dissolved
sufficiently in the solvent to be used in the reaction. To add the alkali or catalyst,
a solution of the alkali or catalyst is added slowly while a reaction solution is
stirred under the atmosphere of an inert gas such as argon and nitrogen, or conversely,
a reaction solution may be slowly added to a solution of the alkali or catalyst.
[0143] When the compound of the present invention is used for producing a light-emitting
device, the purity of the compound influences performance of the light-emitting device
such as a luminescence property. Therefore, a raw material compound before subjected
to polymerization is preferably purified by a method such as distillation, sublimation
or recrystallization and thereafter subjected to polymerization. Further after the
polymerization, purification such as purification by reprecipitation and fractionation
by chromatography is preferably applied.
[0144] When the compound of the present invention is produced, a compound represented by
the above formula (X) is preferably used.
[0145] In the above formula (X), an arylene group, a divalent heterocyclic group and a divalent
aromatic amine group represented by Ar
1, a phenylene group represented by J
1, an alkylene group represented by J
2, and a halogen atom represented by X
1 and X
2 are the same as defined above.
[0146] As the halogen atom represented by X
1 and X
2, in view of easiness of synthesizing the compound to be obtained, a bromine atom
and an iodine atom are preferable and a bromine atom is more preferable.
[0148] Furthermore, the compound represented by the above formula (X) may be produced by
any method. For example, the compound can be produced by a method including reacting
a compound represented by the above formula (XI) and a compound represented by the
above formula (XII) in a base.
[0149] As the base to be used in the above reaction, an inorganic base such as potassium
carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide or an organic
base such as triethylamine is added in an amount of 1 equivalent or more relative
to the above formula (XI) and preferably 1 to 20 equivalents and subjected to the
reaction.
[0150] In the above reaction, usually, a solvent is used. Examples of the solvent include
N,N-dimethylformamide, dimethylsulfoxide, toluene, dimethoxyethane and tetrahydrofuran.
[0151] The reaction temperature of the above reaction is usually 0°C to the boiling point
of the solvent and preferably 50 to 150°C. Furthermore, the reaction time of the above
reaction is 0.5 to 100 hours.
<Composition>
[0152] The composition of the present invention is a composition comprising the compound
of the present invention. For example, a composition comprising at least one selected
from the group consisting of a hole transport material, an electron transport material
and a light-emitting material, and a polymer compound as mentioned above, is mentioned.
[0153] Furthermore, the composition of the present invention can be rendered also to be
a liquid composition further by adding a solvent thereto. More specifically, the liquid
composition of the present invention is a liquid composition containing a polymer
compound as mentioned above and a solvent. Hereinafter, the composition of the present
invention and the liquid composition of the present invention are collectively referred
to as "the liquid composition".
[0154] The liquid composition of the present invention is useful for producing a light-emitting
device such as a light-emitting device and an organic transistor. In the specification,
"the liquid composition" refers to a composition which is present as a liquid state
when a device is produced, and typically refers to a composition present in a liquid
state at normal pressure (more specifically, 1 atm) and at 25°C. Furthermore, the
liquid composition is sometimes generally called as ink, an ink composition and solution,
etc.
[0155] The liquid composition of the present invention may contain, other than a polymer
compound as mentioned above, a low molecular light-emitting material, a hole transport
material, an electron transport material, a stabilizer, additives for controlling
viscosity and/or surface tension and an antioxidant, etc. These optional components
each may be used alone or in combination with two or more types.
[0156] Examples of the low molecular light-emitting material include a naphthalene derivative,
anthracene, an anthracene derivative, perylene, a perylene derivative, a polymethine-based
pigment, a xanthene-based pigment, a coumarin-based pigment, a cyanine-based pigment,
a metal complex containing a metal complex of an 8-hydroxyquinoline as a ligand, a
metal complex containing a metal complex of an 8-hydroxyquinoline derivative as a
ligand, other fluorescent metal complexes, an aromatic amine, tetraphenylcyclopentadiene,
a tetraphenylcyclopentadiene derivative, tetraphenylcyclobutadiene, a tetraphenylcyclobutadiene
derivative, fluorescent materials such as stilbene-, a silicon-containing aromatic-,
oxazole-, furoxan-, thiazole-, tetraarylmethane-, thiadiazole-, pyrazole-, metacyclophane-
and acetylene-based low molecular compounds. In addition, materials described in
JP 57-51781 A and
JP 59-194393 A etc. are included.
[0157] Examples of the hole transport material include polyvinyl carbazole and a derivative
thereof, polysilane and a derivative thereof, a polysiloxane derivative having an
aromatic amine in the side chain or main chain, a pyrazoline derivative, an arylamine
derivative, a stilbene derivative, a triphenyldiamine derivative, polyaniline and
a derivative thereof, polythiophene and a derivative thereof, polypyrrole and a derivative
thereof, poly(p-phenylenevinylene) and a derivative thereof, and poly(2,5-thienylenevinylene)
and a derivative thereof
[0158] Examples of the electron transport material include, an oxadiazole derivative, anthraquinodimethane
and a derivative thereof, benzoquinone and a derivative thereof, naphthoquinone and
a derivative thereof, anthraquinone and a derivative thereof, tetracyanoanthraquinodimethane
and a derivative thereof, a fluorenone derivative, diphenyldicyanoethylene and a derivative
thereof, a diphenoquinone derivative, metal complexes of 8-hydroxyquinoline and a
derivative thereof; polyquinoline and a derivative thereof, polyquinoxaline and a
derivative thereof, and polyfluorene and a derivative thereof.
[0159] Examples of the stabilizer include a phenolic antioxidant and a phosphoric antioxidant.
[0160] As additives for controlling viscosity and/or surface tension, a high molecular-weight
compound (thickening agent) and a poor solvent for increasing viscosity, a low molecular-weight
compound for decreasing viscosity and a surfactant for decreasing surface tension
etc. may be used in appropriate combination.
[0161] As the high molecular-weight compound, any high molecular-weight compound may be
used as long as it does not inhibit light emission and charge transport, and it is
usually a soluble compound in the solvent for a liquid composition. As the high molecular-weight
compound, a high molecular weight polystyrene and a high molecular weight polymethylmethacrylate,
etc. can be used. The polystyrene-equivalent weight average molecular weight of the
high molecular-weight compound is preferably 500,000 or more and more preferably 1,000,000
or more. Furthermore, a poor solvent can be used as a thickening agent.
[0162] As the antioxidant, any antioxidant may be used as long as it does not inhibit light
emission and charge transport, and if a composition contains a solvent, the antioxidant
soluble in the solvent is usually used. Examples of the antioxidant include a phenolic
antioxidant and a phosphoric antioxidant. Storage stability of the polymer compound
and the solvent can be improved by use of the antioxidant.
[0163] When the liquid composition of the present invention contains a hole transport material,
the ratio of the hole transport material in the liquid composition is usually 1 to
80 wt% and preferably 5 to 60 wt%. Furthermore, when the liquid composition of the
present invention contains an electron transport material, the ratio of the electron
transport material in the liquid composition is usually 1 to 80 wt% and preferably
5 to 60 wt%.
[0164] When a film is formed by using the liquid composition in producing a light-emitting
device, after the liquid composition is applied, all that should be done is just removing
a solvent by drying. In addition, when a charge transport material and a light-emitting
material are added, the same procedure can be applied. Therefore, the liquid composition
is extremely favorable in view of production. Note that drying may be performed in
a warm state of about 50 to 150°C or under reduced pressure of about 10
-3 Pa.
[0165] In forming a film using the liquid composition, a coating method can be used such
as a spin coating method, a casting method, a microgravure coating method, a gravure
coating method, a bar coating method, a roll coating method, a wire bar coating method,
a dip coating method, a slit coating method, a cap coating method, a capillary coating
method, a spray coating method, a screen printing method, a flexo printing method,
an offset printing method, an inkjet printing method and a nozzle coating method.
[0166] The ratio of a solvent in the liquid composition is usually 1 to 99.9 wt% relative
to the total weight of the liquid composition, preferably 60 to 99.9 wt% and more
preferably, 90 to 99.8 wt%. The viscosity of the liquid composition, which varies
depending upon the printing method, is preferably 0.5 to 500 mPa·s at 25°C. In the
case where the liquid composition passes through an ejection apparatus as in the case
of inkjet printing method etc., viscosity is preferably 0.5 to 20 mPa·s at 25°C. to
prevent clogging during ejection and bending of sprayed liquid composition.
[0167] As the solvent contained in the liquid composition, a solvent capable of dissolving
or dispersing components of the liquid composition except the solvent is preferable.
Examples of the solvent include chlorine solvents such as chloroform, methylene chloride,
1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and o-dichloro benzene; ether
solvents such as tetrahydrofuran and dioxane; aromatic hydrocarbon solvents such as
toluene, xylene, trimethylbenzene and mesitylene; aliphatic hydrocarbon solvents such
as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane
and n-decane; ketone solvents such as acetone, methylethylketone and cyclohexanone;
ester solvents such as ethyl acetate, butyl acetate, methyl benzoate and ethyl cellosolve
acetate; polyhydric alcohols and a derivative thereof such as ethylene glycol, ethylene
glycol monobutyl ether, ethylene glycol monoethylether, ethylene glycol monomethylether,
dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethylether,
glycerin and 1,2-hexanediol; alcohol solvents such as methanol, ethanol, propanol,
isopropanol and cyclohexanole; sulfoxide solvents such as dimethylsulfoxide; and amide
solvents such as N-methyl-2-pyrrolidone and N,N-dimethylformamide. Furthermore, these
solvents may be used alone or in combination of more than one types. Of the solvents,
one or more organic solvents having a structure having at least one benzene ring and
having a melting point of 0°C or less and a boiling point of 100°C or more is preferably
contained in view of viscosity and film forming property etc. As the type of solvent,
in view of solubility of the components of the liquid composition except the solvent
in an organic solvent, uniformity of the film formed and viscosity property, etc.,
an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, an ester solvent
and a ketone solvent are preferable. Preferable examples thereof include toluene,
xylene, ethylbenzene, diethylbenzene, trimethylbenzene, mesitylene, n-propylbenzene,
isopropylbenzene, n-butylbenzene, isobutylbenzene, s-butylbenzene, anisole, ethoxybenzene,
1-methylnaphthalene, cyclohexane, cyclohexanone, cyclohexyl benzene, bicyclohexyl,
cyclohexenylcyclohexanone, n-heptylcyclohexane, n-hexylcyclohexane, methylbenzoate,
2-propylcyclohexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 2-nonanone,
2-decanone and dicyclohexyl ketone. More preferably, at least one of the solvents
including xylene, anisole, mesitylene, cyclohexylbenzene and bicyclohexylmethylbenzoate,
is contained.
[0168] The number of types of solvents contained in the liquid composition, in view of film
forming property and device characteristic, is preferably 2 or more, more preferably
2 to 3 and particularly preferably 2.
[0169] When 2 types of solvents are contained in the liquid composition, one of the solvents
may be in a solid state at 25°C. In view of film forming property, it is preferable
that one of the solvents has a boiling point of 180°C or more and the other solvent
has a boiling point of less than 180°C. It is more preferable that one of the solvents
has a boiling point of 200°C or more and the other solvent has a boiling point of
less than 180°C. Furthermore, in view of viscosity, 0.2 wt% or more of the components
of the liquid composition from which a solvent is removed is preferably dissolved
in the solvent at 60°C. In one of the two types of solvents, 0.2 wt% or more of the
components of the liquid composition from which a solvent is removed is preferably
dissolved at 25°C.
[0170] When three types of solvents are contained in the liquid composition, one to two
types of solvents may be in a state of solid at 25°C. In view of film forming property,
it is preferable that at least one of the three types of solvents has a boiling point
of 180°C or more and at least one of the solvents has a boiling point of less than
180°C. It is more preferable that at least one of the three types of solvents has
a boiling point of 200°C or more and 300°C or less and at least one of the solvents
has a boiling point of less than 180°C. In view of viscosity, in two types of the
three types of solvents, 0.2 wt% or more of the components of the liquid composition
from which a solvent is removed is preferably dissolved at 60°C. In one of the three
types of solvents, 0.2 wt% or more of the components of the liquid composition from
which a solvent is removed is preferably dissolved at 25°C.
[0171] When two or more types of solvents are contained in the liquid composition, in view
of viscosity and film forming property, the content of the solvent having the highest
boiling point is preferably 40 to 90 wt% of the total solvents contained in the liquid
composition and more preferably 50 to 90 wt% and further preferably 65 to 85 wt%.
<Film>
[0172] A film of the present invention will be described. The film is formed of a polymer
compound as mentioned above. As the type of film, a luminous film, a conductive film
and an organic semiconductor film, etc. are mentioned.
[0173] Furthermore, a film according to a second aspect of the present invention is formed
by crosslinking of the polymer compound. The film is usually hardened by crosslinking
caused by an external stimulus such as heat or light.
[0174] The heat for hardening a film is not particularly limited; however, it generally
falls within the range of room temperature to 300°C. The upper limit thereof is, in
view of easiness of forming a film, preferably 250°C, further preferably 190°C and
most preferably 170°C. Furthermore, the lower limit is, in view of stability of a
film at room temperature, preferably 50°C, further preferably 70°C and most preferably
100°C.
[0175] The light for hardening a film is not particularly limited; however, generally UV
light, near ultra violet light and visible light are used, and UV light and near ultra
violet light are preferable.
[0176] When the film of the present invention is hardened, the hardening rate can be controlled
depending upon the temperature, time or light exposure wavelength and exposure time.
[0177] The luminous film, in view of brightness of a device and emission voltage etc., preferably
has, an emission quantum yield of 50% or more, more preferably 60% or more and further
preferably 70% or more.
[0178] A conductive film preferably has a surface resistance of 1 KΩ/□ or less. The electric
conductivity of the film can be improved by doping a Lewis acid and an ionic compound,
etc. thereto. The surface resistance is more preferably 100Ω/□ or less and further
preferably, 10Ω/□ or less.
[0179] In an organic semiconductor film, a larger one of an electron mobility and a hole
mobility is preferably 10
-5 cm
2/V/second or more, more preferably 10
-3 cm
2/V/second or more and further preferably 10
-1 cm
2/V/second or more. Furthermore, an organic transistor can be produced by using an
organic semiconductor film. Specifically, an organic transistor can be obtained by
forming an organic semiconductor film on an Si substrate having an insulating film
such as SiO
2 and a gate electrode formed thereon, and forming a source electrode and a drain electrode
of Au, etc.
<Organic transistor>
[0180] The organic transistor of the present invention is an organic transistor containing
a compound as mentioned above. Hereinafter, an embodiment of the organic transistor,
that is, a field effect transistor, will be described.
[0181] The compound of the present invention can be suitably used as a material for field
effect transistor, in particular, as a material for an active layer. As the structure
of the field effect transistor, it is usually satisfactory if a source electrode and
a drain electrode are provided in contact with an active layer formed of the compound
of the present invention and a gate electrode is provided so as to sandwich an insulating
layer in contact with the active layer.
[0182] The field effect transistor is usually formed on a supporting substrate. As the supporting
substrate, a glass substrate, a flexible film substrate as well as a plastic substrate
can be used.
[0183] A field effect transistor can be produced by a known method, for example, a method
described in
JP 5-110069 A.
[0184] When an active layer is formed, use of a compound soluble in an organic solvent is
favorable and preferable in view of production. In forming a film from a solution
prepared by dissolving a compound soluble in an organic solvent in a solvent, a spin
coating method, a casting method, a microgravure coating method, a gravure coating
method, a bar coating method, a roll coating method, a wire bar coating method, a
dip coating method, a slit coating method, a cap coating method, a capillary coating
method, a spray coating method, a screen printing method, a flexo printing method,
an offset printing method, an inkjet printing method and a nozzle coating method can
be used.
[0185] After the field effect transistor is produced and preferably encapsulated to form
an encapsulated field effect transistor. By virtue of this, the field effect transistor
can be blocked from the air and suppressed from deterioration of characteristics thereof
[0186] As the encapsulating method, e.g., a method of covering with a UV rays (UV) curable
resin, a thermosetting resin and an inorganic SiONx film, etc. and a method of joining
glass plates and films with a UV rays (UV) curable resin or a thermosetting resin
are mentioned. To effectively block a field effect transistor from the air, it is
preferred to perform steps from production thereof to encapsulation without being
exposed to the air (for example, in a dry nitrogen atmosphere or in vacuum).
<Organic photoelectric transducer>
[0187] An organic photoelectric transducer of the present invention (for example, solar
battery) is an organic photoelectric transducer containing the aforementioned compound.
[0188] The compound of the present invention can be preferably used as a material for an
organic photoelectric transducer, in particular, as an organic semiconductor layer
of a Schottky barrier type device using the interface between an organic semiconductor
and a metal, and furthermore, as an organic semiconductor layer of a pn-heterojunction
type device using the interface between an organic semiconductor and an inorganic
semiconductor or the interface between organic semiconductors.
[0189] Furthermore, the compound of the present invention can be preferably used as an electron
donating compound and an electron receptor compound in a bulk heterojunction device
increased in donor/acceptor contact area, furthermore, an organic photoelectric transducer
using a polymer/low molecular complex system, for example, as an electron donating
conjugated compound (diffusion support) of a bulk heterojunction organic photoelectric
transducer having a fullerene derivative dispersed therein as an electron receptor.
[0190] As a structure of an organic photoelectric transducer, for example, in a pn-heterojunction
device, it is satisfactory if a p-type semiconductor layer is formed on ITO, further
an n-type semiconductor layer is laminated thereon, and an ohm electrode is provided
thereon.
[0191] The organic photoelectric transducer is usually formed on a supporting substrate.
As the supporting substrate, a glass substrate, a flexible film substrate as well
as a plastic substrate can be used.
<Light-emitting device>
[0193] Next, a light-emitting device of the present invention will be described.
[0194] The light-emitting device of the present invention is a light-emitting device having
electrodes comprising an anode and a cathode, and an organic layer provided between
the electrodes and containing the compound of the present invention, preferably a
light-emitting device having an organic layer serving as a light-emitting layer or
a charge transport layer. Examples of the light-emitting device of the present invention
include (1) an light-emitting device having an electron transport layer provided between
a cathode and a light-emitting layer, (2) a light-emitting device having a hole transport
layer provided between an anode and a light-emitting layer and (3) a light-emitting
device having an electron transport layer provided between a cathode and a light-emitting
layer and having a hole transport layer provided between an anode and the light-emitting
layer.
[0195] More specifically, the following structures a) to d) are mentioned.
- a) anode/light-emitting layer/cathode
- b) anode/hole transport layer/light-emitting layer/cathode
- c) anode/light-emitting layer/electron transport layer/cathode
- d) anode/hole transport layer/light-emitting layer/electron transport layer/cathode
(wherein symbol "/" indicates that individual layers are laminated in adjacent to
each other. The same is applied in the following)
[0196] The light-emitting layer is a layer having a function of emitting light. The hole
transport layer is a layer having a function of transporting holes, The electron transport
layer is a layer having a function of transporting electrons. Note that the electron
transport layer and the hole transport layer are collectively called a charge transport
layer. As the light-emitting layer, hole transport layer and electron transport layer
each may consists of two layers or more. Furthermore, the hole transport layer provided
in adjacent to a light-emitting layer is sometimes called as an interlayer.
[0197] As a method for forming a light-emitting layer, a method of forming a film from a
solution is mentioned. In forming a film from a solution, a spin coating method, a
casting method, a microgravure coating method, a gravure coating method, a bar coating
method, a roll coating method, a wire bar coating method, a dip coating method, a
slit coating method, a cap coating method, a capillary coating method, a spray coating
method, a screen printing method, a flexo printing method, an offset printing method,
an inkjet printing method and a nozzle coating method can be used. Note that the formation
of a film from a solution is useful for forming films of a hole transport layer and
an electron transport layer (described later).
[0198] When a film is formed from a solution by using the compound of the present invention
in producing a light-emitting device, all that should be done after the solution is
applied, is just removing a solvent by drying. Furthermore, even in the case where
a charge transport material and a light-emitting material are added, the same procedure
can be applied and thus favorable in production.
[0199] The film thickness of a light-emitting layer, which may be selected such that appropriate
driving voltage and luminous efficiency values are obtained, is, for example, 1 nm
to 1 µm, preferably 2 nm to 500 nm and further preferably 5 nm to 200 nm.
[0200] In the light-emitting device of the present invention, a light-emitting material
except the aforementioned compound may be used in combination in a light-emitting
layer. Furthermore, in the light-emitting device of the present invention, a light-emitting
layer containing a light-emitting material except the aforementioned compound and
a light-emitting layer containing the aforementioned compound may be laminated.
[0201] Examples of a light-emitting material except the aforementioned compound include
low molecular compounds such as a naphthalene derivative, anthracene and a derivative
thereof, perylene and a derivative thereof, pigments including a polymethine-based
pigment, a xanthene-based pigment, a coumarin-based pigment and a cyanine-based pigment,
a metal complex of 8-hydroxyquinoline and a derivative thereof, an aromatic amine,
tetraphenylcyclopentadiene and a derivative thereof and tetraphenylbutadiene and a
derivative thereof In addition, the compounds described in
JP 57-51781 A and
JP 59-194393 A, etc. may be mentioned.
[0202] When the light-emitting device of the present invention has a hole transport layer,
the hole transport material to be used herein is the same as the hole transport material
described in the section of the liquid composition; however, preferable examples thereof
include polymer hole transport materials such as polyvinylcarbazole and a derivative
thereof, polysilane and a derivative thereof, a polysiloxane derivative having an
aromatic amine compound group in the side chain or main chain, polyaniline and a derivative
thereof, polythiophene and a derivative thereof, poly(p-phenylenevinylene) and a derivative
thereof, poly(2,5-tienylenevinylene) and a derivative thereof. More preferable examples
thereof include, polyvinyl carbazole and a derivative thereof, polysilane and a derivative
thereof and a polysiloxane derivative having an aromatic amine in the side chain or
main chain. In the case of a low molecular hole transport material, it is preferably
dispersed in a polymer binder and put in use.
[0203] As a method for forming a hole transport layer, in the case of a low molecular hole
transport material, a method for forming a film from a solution containing a polymer
binder mixed therein is mentioned. Furthermore, in the case of a high-molecular hole
transport material, a method for forming a film from a solution is mentioned.
[0204] As the polymer binder to be mixed, a polymer binder that does not significantly inhibit
charge transport is preferable and a polymer binder that does not significantly absorb
visible light is suitably used. Examples of the polymer binder include polycarbonate,
polyacrylate, polymethylacrylate, polymethylmethacrylate, polystyrene, polyvinyl chloride
and polysiloxane.
[0205] The film thickness of the hole transport layer, which may be selected such that appropriate
driving voltage and luminous efficiency values are obtained, is for example, 1 nm
to 1 µm, preferably 2 nm to 500 nm, and further preferably 5 nm to 200 nm.
[0206] When the light-emitting device of the present invention has an electron transport
layer, the electron transport material to be used is the same as the electron transport
material as described in the section of the liquid composition; however, preferable
examples thereof include an oxadiazole derivative, benzoquinone and a derivative thereof,
anthraquinone and a derivative thereof, a metal complex of 8-hydroxy quinoline and
a derivative thereof, polyquinoline and a derivative thereof, polyquinoxaline and
a derivative thereof and polyfluorene and a derivative thereof; and more preferable
examples thereof include 2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole, benzoquinone,
anthraquinone, tris(8-quinolinol)aluminum and polyquinoline,
[0207] As a method for forming a film of the electron transport layer method, in the case
of a low-molecular electron transport material, a vapor deposition method for forming
a film from a powder, and a method for forming a film from a solution or a molten
state are mentioned; in the case of a high-molecular electron transport material,
a method for forming a film from a solution or a molten state is mentioned. When a
film is formed from a solution or a molten state, a polymer binder may be used in
combination.
[0208] As the polymer binder to be added, a polymer binder that does not significantly inhibit
charge transport is preferable, and a polymer binder that does not significantly absorb
visible light is suitably used. Examples of the polymer binder include poly(N-vinylcarbazole),
polyaniline and a derivative thereof, polythiophene and a derivative thereof, poly(p-phenylenevinylene)
and a derivative thereof, poly(2,5-thienylenevinylene) and a derivative thereof, polycarbonate,
polyacrylate, polymethylacrylate, polymethylmethacrylate, polystyrene, polyvinyl chloride
and polysiloxane.
[0209] The film thickness of the electron transport layer may be selected such that appropriate
driving voltage and luminous efficiency values are obtained, for example, 1 nm to
1 µm, preferably 2 nm to 500 nm, and further preferably 5 nm to 200 nm.
[0210] Furthermore, of the charge transport layers provided in adjacent to an electrode,
a charge transport layer having a function of improving an efficiency of charge injection
from an electrode and having an effect of reducing the driving voltage of a device
is sometimes particularly called a charge injection layer (hole injection layer, electron
injection layer).
[0211] Furthermore, to improve adhesion with an electrode and to improve injection of charge
from an electrode, the charge injection layer or an insulating layer may be provided
in adjacent to the electrode. Moreover, to improve adhesion at the interface and prevent
contamination, etc., a thin buffer layer may be inserted in the interface between
a charge transport layer and a light-emitting layer.
[0212] The order and number of layers to be laminated and the thickness of each layer may
be appropriately selected in consideration of luminous efficiency and device life.
[0213] In the present invention, as a light-emitting device having a charge injection layer
provided therein, a light-emitting device having a charge injection layer provided
in adjacent to a cathode and a light-emitting device having a charge injection layer
provided in adjacent to an anode are mentioned.
[0214] Specific examples thereof include the following structures e) to p).
e) anode/charge injection layer/light-emitting layer/cathode,
f) anode/light-emitting layer/charge injection layer/cathode,
g) anode/charge injection layer/light-emitting layer/charge injection layer/cathode,
h) anode/charge injection layer/hole transport layer/light-emitting layer/cathode,
i) anode/hole transport layer/light-emitting layer/charge injection layer/cathode,
j) anode/charge injection layer/hole transport layer/light-emitting layer/charge injection
layer/cathode,
k) anode/charge injection layer/light-emitting layer/charge transport layer/cathode,
l) anode/light-emitting layer/electron transport layer/charge injection layer/cathode,
m) anode/charge injection layer/light-emitting layer/electron transport layer/charge
injection layer/cathode,
n) anode/charge injection layer/hole transport layer/light-emitting layer/charge transport
layer/cathode,
o) anode/hole transport layer/light-emitting layer/electron transport layer/charge
injection layer/cathode,
p) anode/charge injection layer/hole transport layer/light-emitting layer/electron
transport layer/charge injection layer/cathode.
[0215] Examples of the charge injection layer include a layer containing a conductive polymer;
a layer provided between an anode and a hole transport layer and containing a material
having an intermediate ionization potential value between an anode material and a
hole transport material contained in the hole transport layer, and a layer provided
between a cathode and an electron transport layer and containing a material having
an intermediate affinity value for electron between a cathode material and an electron
transport material contained in the electron transport layer.
[0216] When the charge injection layer is a layer containing a conductive polymer, the electric
conductivity of the conductive polymer is preferably 10
-5 to 10
3 S/cm. To reduce current leakage between emission pixels, the electric conductivity
is more preferably 10
-5 to 10
2 S/cm and further preferably 10
-5 to 10
1 S/cm. Usually, to control the electric conductivity of the conductive polymer to
be 10
-5 to 10
3 S/cm, an appropriately amount of ion is doped in the conductive polymer.
[0217] Type of ion to be doped is anion in the case of a hole injection layer and cation
in the case of an electron injection layer. Examples of the anion include polystyrene
sulfonate ion, alkyl benzene sulfonate ion and camphor sulfonate ion. Examples of
the cations include a lithium ion, a sodium ion, a potassium ion and a tetrabutylammonium
ion.
[0218] The film thickness of the charge injection layer is, for example, 1 nm to 100 nm
and preferably 2 nm to 50 nm.
[0219] Examples of the material to be used for the charge injection layer include polyaniline
and a derivative thereof, polythiophene and a derivative thereof, polypyrrole and
a derivative thereof, polyphenylenevinylene and a derivative thereof, polythienylenevinylene
and a derivative thereof, polyquinoline and a derivative thereof, polyquinoxaline
and a derivative thereof, a conductive polymer such as a polymer having an aromatic
amine structure in the main chain or side chain, metal phthalocyanine (copper phthalocyanine,
etc.) and carbon.
[0220] The insulating layer is a layer having a function of facilitating charge injection.
The average thickness of the insulating layer is, usually, 0.1 to 20 nm, preferably
0.5 to 10 nm and more preferably 1 to 5 nm. Examples of a material for the insulating
layer include a metal fluoride, a metal oxide and an organic insulating material.
As a light-emitting device having an insulating layer provided therein, a light-emitting
device having an insulating layer provided in adjacent to a cathode and a light-emitting
device having an insulating layer provided in adjacent to an anode are mentioned.
[0221] Specific examples thereof include the following structures q) to ab).
q) anode/insulating layer/light-emitting layer/cathode,
r) anode/light-emitting layer/insulating layer/cathode,
s) anode/insulating layer/light-emitting layer/insulating layer/cathode,
t) anode/insulating layer/hole transport layer/light-emitting layer/cathode,
u) anode/hole transport layer/light-emitting layer/insulating layer/cathode,
v) anode/insulating layer/hole transport layer/light-emitting layer/insulating layer/cathode,
w) anode/insulating layer/light-emitting layer/electron transport layer/cathode,
x) anode/light-emitting layer/electron transport layer/insulating layer/cathode,
y) anode/insulating layer/light-emitting layer/electron transport layer/insulating
layer/cathode,
z) anode/insulating layer/hole transport layer/light-emitting layer/electron transport
layer/cathode,
aa) anode/hole transport layer/light-emitting layer/electron transport layer/insulating
layer/cathode,
ab) anode/insulating layer/hole transport layer/light-emitting layer/electron transport
layer/insulating layer/cathode.
[0222] As the substrate for forming the light-emitting device of the present invention,
any substrate may be used as long as it remains unchanged when an electrode is formed
and an organic material layer is formed. Examples of the substrates include glass,
plastic, a polymer film and silicon substrates. In the case of an opaque substrate,
the opposite electrode is preferably transparent or semitransparent.
[0223] In the present invention, at least one of the electrodes comprising an anode and
a cathode is usually transparent or semitransparent and preferably the anode is transparent
or semitransparent.
[0224] As a material for the anode, a conductive metal oxide film and a semitransparent
metal film, etc. are used. More specifically, a film (NESA, etc.) formed of conductive
glass using indium oxide, zinc oxide, tin oxide and a complex thereof, that is, indium/tin/oxide
(ITO) and indium/zinc/oxide, etc. gold, platinum, silver and copper, etc. are used,
and ITO, indium/zinc/oxide and tin oxide are preferable. Examples of a forming method
include a vapor deposition method, a sputtering method, an ion-plating method and
a plating method. Furthermore, as the anode, a transparent conducting film of an organic
substance such as polyaniline and a derivative thereof and polythiophene and a derivative
thereof
[0225] The film thickness of the anode is, in view of light permeability/electric conductivity,
for example, 10 nm to 10 µm, preferably 20 nm to 1 µm and further preferably 50 nm
to 500 nm.
[0226] Furthermore, to facilitate charge injection, a layer formed of e.g., a phthalocyanine
derivative, a conductive polymer or carbon, or a layer formed of e.g., a metal oxide,
a metal fluoride or an organic insulating material may be provided on the anode.
[0227] As a material for the cathode, a material having a small work function is preferable.
Examples thereofthat are used include a metal such as lithium, sodium, potassium,
rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium,
vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium and ytterbium;
an alloy of two or more types of them or an alloy of one or more of them with one
or more of, e.g., gold, silver, platinum, copper, manganese, titanium, cobalt, nickel,
tungsten and tin; and graphite or an graphite intercalation compound. Examples of
the alloy include a magnesium-silver alloy, a magnesium-indium alloy, a magnesium-aluminum
alloy, an indium-silver alloy, a lithium-aluminum alloy, a lithium-magnesium alloy,
a lithium-indium alloy and a calcium-aluminum alloy. The cathode may have a laminate
structure of 2 layers or more.
[0228] The film thickness of the cathode is, in view of electric conductivity and durability,
for example, 10 nm to 10 µm, preferably 20 nm to 1 µm, and further preferably 50 nm
to 500 nm.
[0229] As a method for forming the cathode, a vapor deposition method, a sputtering method
and a laminate method in which a metal film is attached by thermo compression bonding
are used. Furthermore, between the cathode and the organic material layer, a layer
formed of a conductive polymer or a layer formed of a metal oxide, a metal fluoride,
an organic insulating material or the like may be provided. Alternatively after the
cathode is formed, a protecting layer for protecting the light-emitting device may
be attached. To use the light-emitting device stably for a long time, a protecting
layer and/or a protecting cover is preferably attached to protect the device from
the outside.
[0230] As the protecting layer, a resin, a metal oxide, a metal fluoride and a metal borate,
etc. can be used. Furthermore, as the protecting cover, a glass plate, a plastic plate
having a surface treated to lower water permeability, and the like can be used. A
method in which the cover is allowed to adhere airtight to a device substrate with
a thermosetting resin or a light curable resin can be preferably used. If a spacer
is used to keep a space, the device is easily protected from damage. If an inert gas
such as nitrogen and argon is supplied to the space, the cathode can be prevented
from being oxidized. Furthermore, if a desiccating agent such as barium oxide is placed
in the space, the device is easily prevented from damage with a moisture content introduced
by adsorption in a production step. At least one of these measures is preferably employed.
[0231] The light-emitting device of the present invention can be used in displays such as
a surface light source, a segment display, a dot matrix display, a liquid crystal
display (for example, a backlight) and a flat panel feris play.
[0232] To obtain a planer emission by using the light-emitting device of the present invention,
a planar anode and cathode are arranged so as to overlap them. Furthermore, to obtain
patterned emission of light, there are a method of placing a mask having a patterned
window in the surface of the surface light-emitting device, a method of forming an
extremely thick organic material layer in a non light-emitting section such that light
is not substantially emitted, and a method of forming a patterned electrode as either
one of an anode and cathode or both electrodes. Patterns are formed by any one of
these methods and electrodes are arranged so as to independently turn ON/OFF. In this
manner, a segment-type display device capable of displaying numeric characters and
letters, and simple symbols, etc. can be obtained. Furthermore, to obtain a dot matrix
device, an anode and a cathode are formed in the form of stripe and arranged so as
to cross perpendicularly. A partial color display and multi-color display can be realized
by a method of distinctively applying a plurality of types of light-emitting materials
different in luminous color and a method of using a color filter or a fluorescence
conversion filter. A dot matrix device can be passively driven or may be actively
driven in combination with TFT, etc. These display devices can be used as displays
for computers, televisions, mobile terminals, mobile phones, car-navigation and view
finders of video cameras, etc.
[0233] Furthermore, the surface light-emitting device is usually an autonomous light-emitting
thin device and can be preferably used as a surface light source for a backlight of
a liquid crystal display or surface illumination light source. For example, as the
illumination light source, light emission such as white light emission, red light
emission and green light emission or blue light emission are mentioned. Furthermore,
if a flexible substrate is used, the light-emitting device can be used also as a curved-surface
light source and a curved-surface display device.
Examples
[0234] Examples will be shown below to describe the present invention more specifically;
however, the present invention is not limited to these.
<Synthesis Example 1> (Synthesis of compound M-1)
[0235]
[0236] Under an argon atmosphere, divinylcarbinol (25.24 g), triethyl orthoacetate (340
g) and propionic acid (0.20 g) were blended and warmed to 130°C for 4 hours while
removing ethanol by use of Dean-Stark. After completion of the reaction, the resultant
reaction solution was cooled. To the reaction solution, hexane (300 ml) and ion-exchanged
water (300 ml) were added, and stirred at 60°C for 3 hours. After layers were separated,
an organic layer was washed with ion-exchanged water (300 ml × 3 times) and dried
over sodium sulfate. The resultant organic layer was concentrated by passing it through
an alumina flush column. To the resultant oil, again, hexane (300 ml), ion-exchanged
water (300 ml) and propionic acid (0.20 g) were added and stirred at 60°C for 8 hours.
After layers were separated, an organic layer was washed with ion-exchanged water
(300 ml × 3 times) and dried over sodium sulfate. The resultant organic layer was
concentrated by passing it through an alumina flush column to obtain compound M-1
(28 g) represented by the above formula M-1.
1H-NMR (270 MHz, CDCl
3): δ=1.25 (t, 3H), 2.07 (q, 2H), 2.41 (m, 4H), 5.05 (dd, 2H), 5.70 (m, 1H), 6.09 (dd,
1H), 6.29 (m, 1H) ppm.
<Synthesis Example 2> (Synthesis of compound M-2)
[0237]
[0238] Under an argon atmosphere, compound M-1 (14.65 g) and diethyl ether (770 ml) were
blended and cooled to 0°C. Subsequently, to the resultant solution mixture, a 1 M
lithium aluminum hydride ether solution (50 ml) was added dropwise for one hour and
stirred for one hour while the temperature was kept at 0°C. To the resultant reaction
solution, a 5 wt% aqueous sodium hydroxide solution (100 ml) was slowly added dropwise
and quenched. Thereafter, an organic layer was washed with water (100 ml × 3 times)
and the organic layer was dried over sodium sulfate. The resultant organic layer was
concentrated by passing it through an alumina flush column to obtain compound M-2
(8.0 g) represented by the above formula M-2.
1H-NMR (270 MHz, CDCl
3): δ=1.67 (tt, 2H), 2.13-2.28 (m, 3H), 3.63 (q, 2H), 5.04 (dd, 2H), 5.72 (dd, 1H),
6.07 (dd, 1H), 6.30 (m, 1H) ppm.
<Synthesis Example 3> (Synthesis of compound M-3)
[0239]
[0240] Under an argon atmosphere, compound M-2 (18.98 g) and dichloromethane (730 ml) were
blended and cooled to 0°C. To the resultant solution mixture, triethylamine (58 ml)
was added dropwise and then methane sulfonylchloride (24 ml) was added dropwise and
stirred for 2 hours while the temperature was kept at 0°C. To the resultant reaction
solution, water was added and quenched and thereafter, extraction with ether and dehydration
over sodium sulfate were performed to obtain yellow oil (32 g).
[0241] Under an argon atmosphere, the yellow oil (32 g), lithium bromide (36 g) and THF
(400 ml) were blended and refluxed for 7 hours. The resultant reaction solution was
cooled and ion-exchanged water (200 ml) and toluene (500 ml) were added and then,
layers were separated. The organic layer was washed with ion-exchanged water (100
ml × 5 times) and dried over sodium sulfate. The resultant organic layer was concentrated.
After hexane (100 ml) was added, the organic layer was concentrated by passing it
through an alumina flush column. The resultant oil was fractionated (3 mmHg, 27°C)
to obtain compound M-3 (15.1 g) represented by the above formula M-3.
1H-NMR (270 MHz, CDCl
3): δ=1.96 (tt, 2H), 2.22-2.29 (m, 2H), 3.41 (t, 2H), 5.05 (dd, 2H), 5.65 (m, 1H),
6.10 (dd, 1H), 6.30 (m, 1H) ppm.
<Example 1> (Synthesis of compound M-4)
[0242]
[0243] Under an argon atmosphere, in a 300 mL four-neck flask, compound M-3 (5.29 g), 2,7-dibromofluorene
(4.67 g) and DMSO (35 ml) were blended. To the resultant solution mixture, potassium
hydroxide (3.43 g) and potassium iodide (0.17 g) mashed in a mortar were added and
warmed at 85°C for 45 minutes. To the resultant solution mixture, ion-exchanged water
(50 ml) and ethyl acetate (100 ml) were added and then layers were separated. The
organic layer was washed with a saturated saline solution (100 ml x 10 times), dried
over sodium sulfate and then concentrated. The resultant oil was purified by silica
gel column chromatography (developing solvent: hexane) to obtain compound M-4 (4.9
g) represented by the above formula M-4 as a white solid substance.
1H-NMR (270 MHz, CDCl
3): δ=0.68 (m, 4H), 1.81-1.96 (m, 8H), 4.99 (dd, 4H), 5.44 (m, 2H), 5.89 (dd, 2H),
6.22 (td, 2H), 7.47 (m, 6H) ppm.
MS (APCI-MS: Positive) m/z: 512 ([M]
+).
<Example 2> (Synthesis of compound M-5)
[0244]
[0245] Under an argon atmosphere, in a 100 mL four-neck flask, compound M-3 (1.88 g), 2,5-dibromohydroquinone
(2.51 g) and ethanol (7 ml) were blended. To the resultant solution mixture, potassium
hydroxide (0.97 g) mashed in a mortar was added and warmed at 85°C for 9 hours. After
completion of the reaction, to the resultant reaction solution, ion-exchanged water
(20 ml) and ethyl acetate (20 ml) were added and layers were separated. Thereafter,
the organic layer was washed with ion-exchanged water (40 ml × 3 times), dried over
sodium sulfate and then concentrated. The resultant oil was purified by silica gel
column chromatography (developing solvent: toluene/hexane = 1:1) to obtain compound
M-5 (1.3 g) represented by the above formula M-5 as a white solid substance.
1H-NMR (270 MHz, CDCl
3): δ=1.87-1.96 (m, 4H), 2.28-2.35 (m, 4H), 3.94 (t, 4H), 5.05 (dd, 4H), 5.75 (m, 2H),
6.10 (m, 2H), 6.31 (m, 2H), 7.08 (s, 2H) ppm.
<Example 3> (Synthesis of compound M-7)
[0246]
[0247] Under an argon atmosphere, in a 100 mL four-neck flask, compound M-3 (1.63 g), compound
M-6 (1.63 g) represented by the above formula M-6 and ethanol (7 ml) were blended.
To the resultant solution mixture, potassium hydroxide (0.97 g) mashed in a mortar
was added and warmed at 60°C for 40 hours. After completion of the reaction, to the
resultant reaction solution, ion-exchanged water (50 ml) and toluene (50 ml) were
added. After layers were separated, an organic layer was washed with ion-exchanged
water (40 ml × 3 times), dried over sodium sulfate and then concentrated. The resultant
oil was purified by silica gel column chromatography (developing solvent: toluene/hexane
= 1:1) to obtain compound M-7 (1.1 g) represented by the above formula M-7 as a white
solid substance.
[0248] Note that compound M-6 was synthesized with reference to
EP1344788.
1H-NMR (270 MHz, CDCl
3): δ=1.97-2.06 (m, 4H), 2.36-2.43 (m, 4H), 4.10 (t, 4H), 5.04 (dd, 4H), 5.78 (m, 2H),
6.14 (m, 2H), 6.32 (m, 2H), 7.32 (s, 2H), 7.73 (s, 2H) ppm.
<Synthesis Example 4> (Synthesis of compound M-8)
[0249]
[0250] Under nitrogen gas atmosphere, to a mixture of 2,7-dibromofluorene (75 g, 0.22 mol),
hexylbenzene (334 ml) and trifluoromethanesulfonic acid (42 ml) stirred at room temperature,
sodium 3-mercaptopropanesulfonate (8.1 g) was added and stirred at 45°C for 9 hours.
The resultant reaction solution was cooled to room temperature and then added to hexane
(1 L). Excess hexyl benzene was distilled away by distillation under reduced pressure
(105.5°C, 20 hPa), diluted with hexane and then added to methanol. The precipitated
2,7-dibromofluorenone was removed by filtration. The resultant filtrate was concentrated
and then diluted with toluene, and isopropyl alcohol was added to precipitate a solid
substance. The resultant solid substance was recrystallized from toluene/isopropyl
alcohol to obtain compound M-8 (53 g) represented by the above formula M-8 as a white
solid substance.
1H-NMR (270 MHz, CDCl
3): δ=0.88 (t, 3H), 1.20-1.45 (m, 6H), 1.54-1.62 (m, 2H), 2.57 (t, 2H), 4.96 (s, 1H),
6.94 (d, 2H), 7.10 (d, 2H), 7.42 (s, 2H), 7.48 (dd, 2H), 7.60 (d, 2H) ppm.
<Example 4> (Synthesis of compound M-9)
[0251]
[0252] Under an argon atmosphere, in a 100 mL four-neck flask, compound M-3 (0.96 g), compound
M-8 (2.42 g) and dimethylsulfoxide (12 ml) were blended. To the resultant solution
mixture, potassium hydroxide (1.2 g) and potassium iodide (0.08 g) mashed in a mortar
were added and stirred at room temperature for 5 hours. After completion of the reaction,
to the resultant reaction solution, ion-exchanged water (20 ml) and toluene (30 ml)
were added. After layers were separated, an organic layer was washed with a saturated
saline solution (30 ml × 10 times) and dried over sodium sulfate and then concentrated.
The resultant oil was purified by silica gel column chromatography (developing solvent:
toluene/hexane = 1:10) to obtain compound M-9 (2.0 g) represented by the above formula
M-9 as colorless oil.
1H-NMR (270 MHz, CDCl
3): δ=0.75-0.87 (m, 5H), 1.20-1.39 (m, 6H), 1.52-1.56 (m, 2H), 2.00-2.31 (m, 2H), 2.37-2.44
(m, 2H), 2.50-2.56 (t, 2H), 4.92-5.10 (dd, 2H), 5.44-5.53 (td, 1H), 5.89-5.97 (dd,
1H), 6.17-6.30 (td, 1H), 7.00-7.16 (m, 4H), 7.18-7.28 (dd, 2H), 7.47 (d, 2H), 7.55
(d, 2H) ppm.
<Example 5> (Synthesis of compound M-11)
[0253]
[0254] Under an argon atmosphere, in a 300 mL three-neck flask, compound M-10 (5.1 g), compound
M-3 (3.7 g) and dimethylsulfoxide (100 ml) were blended. To this, potassium hydroxide
(1.4 g) was added and stirred at room temperature for 6 hours. After completion of
the reaction, water (30 ml) was added. After layers were separated, the resultant
organic layer was washed with water, then dried over sodium sulfate, and concentrated
to dryness. Subsequently, purification was performed by column chromatography using
hexane: chloroform (= 6:1) as a developing solvent and silica gel as a filler. Recrystallization
was performed to obtain compound M-11 represented by the above formula.
[0255] Note that compound M-10 was synthesized with reference to
U. S. Pat. No. US5447960.
1H-NMR (270 MHz, CDCl
3); 1.88 (m, 4H), 2.26 (q, 4H)), 3.93 (t, 4H), 5.15-4.95 (m, 4H), 5.76-5.66 (m, 2H),
6.33-6.27 (m, 2H), 6.75 (d, 4H), 7.03 (d, 4H), 7.57-7.43 (m, 6H).
<Synthesis Example 5> (Synthesis of compound MM-1)
[0256]
[0257] Under an argon atmosphere, in a 500 ml four-neck flask, 2,7-dibromofluorene (22.7
g), 5-bromo-1-octene (21.9 g), potassium hydroxide (16.7 g), potassium iodide (1.2
g) and dimethylsulfoxide (170 ml) were blended and warmed to 80°C for 4 hours. After
completion of the reaction, the resultant reaction solution was cooled to room temperature.
To this, water (300 ml) and toluene (300 ml) were added and layers were separated.
Subsequently, the organic layer was washed 5 times with a saturated aqueous sodium
chloride solution (300 ml). After the resultant organic layer was dried over sodium
sulfate, purification was performed by column chromatography using hexane as a developing
solvent and silica gel as a filler to obtain compound MM-1 represented by the above
formula MM-1.
ESI-MS: 460 [M]
+
1H-NMR (270 MHz, CDCl
3); δ=0.69 (t, 4H), 1.83 (m, 4H), 1.93 (m, 4H), 4.85 (d, 4H), 5.56 (m, 2H), 7.44-7.53
(m, 6H).
<Synthesis Example 6> (Synthesis of compound MM-3)
[0258]
[0259] Under an argon atmosphere, in a 300 ml three-neck flask, 2,7-dibromofluorene (8.1
g), 8-bromo-1-octene (10.0 g), potassium hydroxide (6.0 g), potassium iodide (0.42
g) and dimethylsulfoxide (60 ml) were blended and warmed to 80°C for 4 hours. After
completion of the reaction, the reaction solution was cooled to room temperature.
To this, water (100 ml) and toluene (100 ml) were blended. After layers were separated,
the resultant organic layer was washed 5 times with a saturated aqueous sodium chloride
solution (100 ml). After the resultant organic layer was dried over sodium sulfate,
purification was performed by column chromatography using hexane as a developing solvent
and silica gel as a filler to obtain compound MM-3 represented by the above formula
MM-3.
ESI-MS: 544 [M]
+
1H-NMR (270 MHz, CDCl
3); δ=0.58 (m, 4H), 1.06 (m, 8H), 1.18 (m, 4H), 1.92 (m, 8H), 4.90 (d, 4H), 5.73 (m,
2H), 7.43-7.52 (m, 6H).
<Synthesis Example 7> (Synthesis of compound MM-X)
[0260]
[0261] A 5 L-three-neck flask was purged with nitrogen. 1-Bromo-3-n-hexylbenzene (226 g)
was weighed and dissolved in a 2.5 L dewatered THF. This solution was cooled to -
75°C or less and a 2.5 M n-butyllithium/hexane solution (358 ml) was added dropwise
and stirred for 5 hours while the temperature was kept at -75°C or less. To this solution,
a solution of 2-methoxycarbonyl-4,4'-dibromobiphenyl (150 g) dissolved in 400 ml of
dewatered THF was added dropwise while the temperature was kept at -70°C or less.
The solution was gradually increased to room temperature and then stirred overnight.
While the reaction solution was stirred at 0°C, 150 ml of water was added dropwise.
After a solvent was distilled away, water (200 ml) was added to the residue. Extraction
was performed once with hexane (1 L) and twice with hexane (100 ml). Organic layers
were combined and washed with a saturated saline solution (200 ml). The water layer
was re-extracted with hexane (100 ml) and then, dried over magnesium sulfate. The
solvent was distilled away to obtain a crude product (264 g) of compound MM-X and
used in the next step without purification.
[0263] <Synthesis Example 8> (Synthesis of compound MM-Y)
[0264] In a 3 L-three neck flask, compound MM-X (264 g) synthesized above was weighed, dissolved
in dichloromethane (900 ml) and purged with nitrogen. This solution was cooled to
0°C or less and a boron trifluoride diethyl ether complex (245 ml) was added dropwise
while the temperature was kept at 5°C or less. After the solution was slowly increased
to room temperature, it was stirred overnight. This reaction solution was poured in
a 2 L of ice water while stirring and stirred for 30 minutes. The layers were separated
and the water layer was extracted with 100 ml of dichloromethane. Organic layers were
combined and a 10% aqueous potassium phosphate solution (1 L) was added and then layers
were separated. The organic layer was washed twice with water (1 L), dried over magnesium
sulfate and then the solvent was distilled away. The resultant oil was dissolved in
200 ml of toluene and passed through a glass filter lined with silica gel to filtrate.
After the solvent was distilled away, 500 ml of methanol was added and vigorously
stirred. The resultant crystal was filtrated and washed with methanol. Recrystallization
was performed from a solvent mixture of hexane/butyl acetate to obtain compound MM-Y
(121 g).
1H-NMR (300 MHz, CDCl
3); δ0.86 (6H, t), 1.26 (12H, m), 1.52 (4H, m), 2.51 (4H t), 6.87 (2H, d), 7.00 (2H,
s), 7.04 (2H, d), 7.12 (2H, t), 7.46 (2H, dd), 7.48 (2H, d), 7.55 (2H, d) ppm.
<Synthesis Example 9> (Synthesis of compound MM-5)
[0265]
[0266] In a 2 L three-neck flask, compound MM-Y (50 g) was weighted and purged with nitrogen.
Dewatered THF (500 ml) was added and cooled to -70°C or less. While the solution was
kept at -70°C or less, a 2.5 M n-butyl lithium/hexane solution (68 ml) was added dropwise.
After dropwise addition, the solution was stirred for 4 hours while keeping the temperature.
2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (44 ml) was added and then the
solution was slowly increased to room temperature and stirred overnight. The solution
was cooled to - 30°C and a 2 M hydrochloric acid/diethyl ether solution (78 ml) was
added dropwise thereto and then the temperature of the solution was increased to room
temperature. After the solvent was distilled away, the resultant substance was dissolved
by adding toluene (400 ml) and filtrated by passing it through a glass filter lined
with silica gel. When the solvent of the resultant solution was distilled away to
obtain a crude product (50 g). Under a nitrogen atmosphere, recrystallization was
performed from a toluene/acetonitrile solvent to obtain 34 g of compound MM-5.
1H-NMR (300 MHz, CDCl
3); δ0.86 (6H, t), 1.26-1.29 (12H, m), 1.31 (24H s), 1.52-1.53 (4H, m), 2.50 (4H, t),
6.92 (2H, d), 7.00 (2H, d), 7.08 (2H, t), 7.13 (2H, s), 7.77 (2H, d), 7.81-7.82 (4H,
m) ppm.
<Example 6> (Synthesis of polymer compound P-1)
[0267] Under an inert gas atmosphere, 2,7-bis(1,3,2-dioxaborolan-2-yl)-9,9-dioctylfluorene
(1.06 g), 2,7-dibromo-9,9-dioctylfluorene (0.22 g), bis(4-bromophenyl)-(4-sec-butylphenyl)-amine
(0.55 g), compound M-4 (0.20 g), bis triphenylphosphine palladium dichloride (1.4
mg), trioctylmethylammonium chloride (trade name: Aliquat 336, manufactured by Aldrich)
(0.25 g) and toluene (40 ml) were blended and heated to 105°C. To the resultant reaction
solution, a 2 M aqueous sodium carbonate solution (6 ml) was added dropwise and refluxed
for 15 hours. After completion of the reaction, phenylboric acid (240 mg) was added
and refluxed for further 4 hours. Subsequently, to this, a 1.8 M aqueous sodium diethyldithiacarbamate
solution (10 ml) was added and stirred at 80°C for 4 hours. The resultant reaction
solution was cooled to room temperature, then washed three times with water (30 ml),
three times with a 3 wt% aqueous acetic acid solution (30 ml) and three times with
water (30 ml), and purified by passing it through an alumina column and a silica gel
column. The resultant toluene solution was added dropwise to methanol (300 ml) and
stirred for one hour. Thereafter, the resultant solid substance was filtrated and
dried to obtain polymer compound P-1 (0.7 g) represented by the following formula:
wherein the numbers attached outside parentheses each represent a molar ratio of a
repeating unit.
[0268] The polystyrene-equivalent number average molecular weight of polymer compound P-1
was 1.1 × 10
5 and the polystyrene-equivalent weight average molecular weight thereof was 3.8 ×
10
5.
[0269] Note that bis(4-bromophenyl)-(4-sec-butylphenyl)-amine was synthesized by a method
described in
WO2002/045184.
<Example 7> (Synthesis of polymer compound P-2)
[0270] Under an inert gas atmosphere, 2,7-bis(1,3,2-dioxaborolan-2-yl)-9,9-dioctylfluorene
(1.05 g), 2,7-dibromo-9,9-dioctylfluorene (0.77 g), compound M-4 (0.31 g), bis triphenylphosphine
palladium dichloride (1.4 mg), trioctylmethylammonium chloride (trade name: Aliquat
336, manufactured by Aldrich) (0.25 g) and toluene (40 ml) were blended and heated
to 105°C. To the resultant reaction solution, a 2 M aqueous sodium carbonate solution
(6 ml) was added dropwise and refluxed for 20 hours. After completion of the reaction,
to this, phenylboric acid (240 mg) was added and refluxed for further 4 hours. Subsequently,
to this, a 1.8 M aqueous sodium diethyldithiacarbamate solution (10 ml) was added
and stirred at 80°C for 4 hours. The resultant reaction solution was cooled to room
temperature, then washed three times with water (30 ml), three times with a 3 wt%
aqueous acetic acid solution (30 ml) and three times with water (30 ml), and purified
by passing it through an alumina column and a silica gel column. The resultant toluene
solution was added dropwise to methanol (300 ml) and stirred for one hour. Thereafter,
the resultant solid substance was filtrated and dried to obtain polymer compound P-2
(0.8 g) represented by the following formula:
wherein the numbers attached outside parentheses each represent a molar ratio of a
repeating unit.
[0271] The polystyrene-equivalent number average molecular weight of polymer compound P-2
was 4.1 × 10
4 and the polystyrene-equivalent weight average molecular weight thereof was 1.3 ×
10
5.
<Example 8> (Synthesis of polymer compound P-3)
[0272] Under an inert gas atmosphere, 2,7-bis(1,3,2-dioxaborolan-2-yl)-9,9-dioctylfluorene
(1.06 g), 2,7-dibromo-9,9-dioctylfluorene (0.66 g), N,N'-bis-(4-bromophenyl)-bis-(4-butylphenyl)-p-phenylenediamine
(0.14 g), compound M-4 (0.20 g), compound MM-1 (0.09 g), palladium acetate (0.4 mg),
tris(o-methoxyphenyl)phosphine (2.8 mg), trioctylmethylammonium chloride (trade name:
Aliquat 336, manufactured by Aldrich) (0.25 g) and toluene (40 ml) were blended and
heated to 105°C. To the resultant reaction solution, a 2 M aqueous sodium carbonate
solution (11 ml) was added dropwise and refluxed for 18 hours. After completion of
the reaction, to this, phenylboric acid (240 mg) was added and refluxed for further
4 hours. Subsequently, to this, a 1.8 M aqueous sodium diethyldithiacarbamate solution
(10 ml) was added and stirred at 80°C for 4 hours. The resultant reaction solution
was cooled to room temperature, then washed three times with water (30 ml), three
times with a 3 wt% aqueous acetic acid solution (30 ml) and three times with water
(30 ml), and purified by passing it through an alumina column and a silica gel column.
The resultant toluene solution was added dropwise to methanol (300 ml) and stirred
for one hour. Thereafter, the resultant solid substance was filtrated and dried to
obtain polymer compound P-3 (0.7 g) represented by the following formula:
wherein the numbers attached outside parentheses each represent a molar ratio of a
repeating unit.
[0273] The polystyrene-equivalent number average molecular weight of polymer compound P-3
was 1.2 × 10
5 and the polystyrene-equivalent weight average molecular weight thereof was 3.9 ×
10
5.
<Example 9> (Synthesis of polymer compound P-4)
[0274] Under an inert gas atmosphere, 2,7-bis(1,3,2-dioxaborolan-2-yl)-9,9-dioctylfluorene
(1.05 g), 2,7-dibromo-9,9-dioctylfluorene (0.55 g), compound MM-4 (0.55 g) represented
by the following formula (MM-4):
compound M-5 (0.09 g), palladium acetate (0.4 mg), tris(o-methoxyphenyl)phosphine
(2.8 mg), trioctylmethylammonium chloride (trade name: Aliquat 336, manufactured by
Aldrich) (0.25 g) and toluene (40 ml) were blended and heated to 105°C. To the resultant
reaction solution, a 2 M aqueous sodium carbonate solution (11 ml) was added dropwise
and refluxed for 22 hours. After completion of the reaction, to this, phenylboric
acid (240 mg) was added and refluxed for further 4 hours. Subsequently, to this, a
1.8 M aqueous sodium diethyldithiacarbamate solution (10 ml) was added and stirred
at 80°C for 4 hours. The resultant reaction solution was cooled to room temperature,
then washed three times with water (30 ml), three times with a 3 wt% aqueous acetic
acid solution (30 ml) and three times with water (30 ml), and purified by passing
it through an alumina column and a silica gel column. The resultant toluene solution
was added dropwise to methanol (300 ml) and stirred for one hour. Thereafter, the
resultant solid substance was filtrated and dried to obtain polymer compound P-5 (0.7
g) represented by the following formula:
wherein the numbers attached outside parentheses each represent a molar ratio of a
repeating unit.
[0275] The polystyrene-equivalent number average molecular weight of polymer compound P-5
was 4.2 x 10
4 and the polystyrene-equivalent weight average molecular weight thereof was 7.5 ×
10
4.
[0276] Note that compound MM-4 was synthesized by a method described in
EP1310539.
<Example 10> (Synthesis of polymer compound P-5)
[0277] Under an inert gas atmosphere, 2,7-bis(1,3,2-dioxaborolan-2-yl)-9,9-dioctylfluorene
(1.06 g), 2,7-dibromo-9,9-dioctylfluorene (0.66 g), compound M-7 (0.55 g), palladium
acetate (0.4 mg), tris(o-methoxyphenyl)phosphine (2.8 mg), trioctylmethylammonium
chloride (trade name: Aliquat 336, manufactured by Aldrich) (0.25 g) and toluene (40
ml) were blended and heated to 105°C. To the resultant reaction solution, a 2 M aqueous
sodium carbonate solution (11 ml) was added dropwise and refluxed for 4 hours. After
completion of the reaction, to this, phenylboric acid (240 mg) was added and refluxed
for further 4 hours. Subsequently, to this, a 1.8 M aqueous sodium diethyldithiacarbamate
solution (10 ml) was added and stirred at 80°C for 4 hours. The resultant reaction
solution was cooled to room temperature, then washed three times with water (30 ml),
three times with a 3 wt% aqueous acetic acid solution (30 ml) and three times with
water (30 ml), and purified by passing it through an alumina column and a silica gel
column. The resultant toluene solution was added dropwise to methanol (300 ml) and
stirred for one hour. Thereafter, the resultant solid substance was filtrated and
dried to obtain polymer compound P-6 (0.9 g) represented by the following formula:
wherein the numbers attached outside parentheses each represent a molar ratio of a
repeating unit.
[0278] The polystyrene-equivalent number average molecular weight of polymer compound P-6
was 1.0 × 10
5 and the polystyrene-equivalent weight average molecular weight thereof was 3.9 ×
10
5.
<Example 11> (Synthesis of polymer compound P-6)
[0279] Under an inert gas atmosphere, the compound (1.48 g) represented by the following
formula (MM-5):
2,7-dibromo-9,9-dioctylfluorene (0.22 g), the compound (0.82 g) represented by the
above formula (MM-4), compound (M-9) (0.23 g), palladium acetate (0.4 mg), tris(o-methoxyphenyl)phosphine
(2.8 mg) and toluene (44 ml) were blended and heated to 105°C. To the resultant reaction
solution, a 20% aqueous tetraethyl ammonium hydroxide solution (6.6 ml) was added
dropwise and refluxed for 4 hours. After completion of the reaction, to this, phenylboric
acid (240 mg) was added and refluxed for further 18 hours. Subsequently, to this,
a 1.8 M aqueous sodium diethyldithiacarbamate solution (22 ml) was added and stirred
at 80°C for 4 hours. The resultant reaction solution was cooled to room temperature,
then washed three times with water (30 ml), three times with a 3 wt% aqueous acetic
acid solution (30 ml) and three times with water (30 ml), and purified by passing
it through an alumina column and a silica gel column. The resultant toluene solution
was added dropwise to methanol (300 ml) and stirred for one hour and thereafter, the
resultant solid substance was filtrated and dried to obtain polymer compound P-6 (1.5
g) represented by the following formula:
wherein the numbers attached outside parentheses each represent a molar ratio of a
repeating unit.
[0280] The polystyrene-equivalent number average molecular weight of polymer compound P-6
was 2.2 x 10
5 and the polystyrene-equivalent weight average molecular weight thereof was 8.5 ×
10
5.
<Example 12> (Synthesis of polymer compound P-7)
[0281] Under an inert gas atmosphere, the compound (1.48 g) represented by the above formula
(MM-5), 2,7-dibromo-9,9-dioctylfluorene (0.22 g), the compound (0.82 g) represented
by the above formula (MM-4), compound (M-4) (0.20 g), palladium acetate (0.4 mg),
tris(o-methoxyphenyl)phosphine (2.8 mg) and toluene (44 ml) were blended and heated
to 105°C. To the resultant reaction solution, a 20% aqueous tetraethyl ammonium hydroxide
solution (6.6 ml) was added dropwise and refluxed for 18 hours. After completion of
the reaction, to this, phenylboric acid (240 mg) was added and refluxed for further
4 hours. Subsequently, to this, a 1.8 M aqueous sodium diethyldithiacarbamate solution
(22 ml) was added and stirred at 80°C for 4 hours. The resultant reaction solution
was cooled to room temperature, then washed three times with water (30 ml), three
times with a 3 wt% aqueous acetic acid solution (30 ml) and three times with water
(30 ml), and purified by passing it through an alumina column and a silica gel column.
The resultant toluene solution was added dropwise to methanol (300 ml) and stirred
for one hour and thereafter, the resultant solid substance was filtrated and dried
to obtain polymer compound P-7 (1.3 g) represented by the following formula:
wherein the numbers attached outside parentheses each represent a molar ratio of a
repeating unit.
[0282] The polystyrene-equivalent number average molecular weight of polymer compound P-7
was 5.1 × 10
4 and the polystyrene-equivalent weight average molecular weight thereof was 1.0 ×
10
5.
<Comparative Example 1> (Synthesis of polymer compound CP-1)
[0283] Under an inert gas atmosphere, 2,7-bis(1,3,2-dioxaborolan-2-yl)-9,9-dioctylfluorene
(1.06 g), bis(4-bromophenyl)-(4-sec-butylphenyl)-amine (0.87 g), compound MM-6 (0.04
g) represented by the following formula (MM-6):
bis triphenylphosphine palladium dichloride (1.4 mg), trioctylmethylammonium chloride
(trade name: Aliquat 336, manufactured by Aldrich) (0.25 g) and toluene (40 ml) were
blended and heated to 105°C. To the resultant reaction solution, a 2 M aqueous sodium
carbonate solution (6 ml) was added dropwise and refluxed for 7 hours.
[0284] After completion of the reaction, to this, phenylboric acid (240 mg) was added and
refluxed for further 4 hours. Subsequently, to this, a 1.8 M aqueous sodium diethyldithiacarbamate
solution (10 ml) was added and stirred at 80°C for 4 hours. The resultant reaction
solution was cooled to room temperature, then washed three times with water (30 ml),
three times with a 3 wt% aqueous acetic acid solution (30 ml) and three times with
water (30 ml), and purified by passing it through an alumina column and a silica gel
column. The resultant toluene solution was added dropwise to methanol (300 ml) and
stirred for one hour. Thereafter, the resultant solid substance was filtrated and
dried to obtain polymer compound CP-1 (0.8 g) represented by the following formula:
wherein the numbers attached outside parentheses each represent a molar ratio of a
repeating unit.
[0285] The polystyrene-equivalent number average molecular weight of polymer compound CP-1
was 3.4 × 10
4 and the polystyrene-equivalent weight average molecular weight thereof was 6.7 ×
10
4.
[0286] Note that compound MM-6 was synthesized by a method described in
US2004/035221.
<Comparative Example 2> (Synthesis of polymer compound CP-2)
[0287] Under an inert gas atmosphere, 2,7-bis(1,3,2-dioxaborolan-2-yl)-9,9-dioctylfluorene
(1.06 g), 2,7-dibromo-9,9-dioctylfluorene (0.22 g), bis(4-bromophenyl)-(4-sec-butylphenyl)-amine
(0.55 g), compound MM-2 (0.21 g) represented by the following formula (MM-2):
bis triphenylphosphine palladium dichloride (1.4 mg), trioctylmethylammonium chloride
(trade name: Aliquat 336, manufactured by Aldrich) (0.25 g) and toluene (40 ml) were
blended and heated to 105°C. To the resultant reaction solution, a 2 M aqueous sodium
carbonate solution (6 ml) was added dropwise and refluxed for 7 hours. After completion
of the reaction, to this, phenylboric acid (240 mg) was added and refluxed for further
4 hours. Subsequently, to this, a 1.8 M aqueous sodium diethyldithiacarbamate solution
(10 ml) was added and stirred at 80°C for 4 hours. The resultant reaction solution
was cooled to room temperature, then washed three times with water (30 ml), three
times with a 3 wt% aqueous acetic acid solution (30 ml) and three times with water
(30 ml) and purified by passing it through an alumina column and a silica gel column.
The resultant toluene solution was added dropwise to methanol (300 ml) and stirred
for one hour. Thereafter, the resultant solid substance was filtrated and dried to
obtain polymer compound CP-2 (yield 0.9 g) represented by the following formula:
wherein the numbers attached outside parentheses each represent a molar ratio of a
repeating unit.
[0288] The polystyrene-equivalent number average molecular weight of polymer compound CP-2
was 8.4 × 10
4 and the polystyrene-equivalent weight average molecular weight thereof was 2.0 ×
10
5.
[0289] Note that compound MM-2 was synthesized by a method described in
JP 2008-106241 A
<Comparative Example 3> (Synthesis of polymer compound CP-3)
[0290] Under an inert gas atmosphere, 2,7-bis(1,3,2-dioxaborolan-2-yl)-9,9-dioctylfluorene
(1.06 g), compound MM-3 (0.22 g) represented by the above formula MM-3, N,N-di(4-bromophenyl)aniline
(0.73 g), bis triphenylphosphine palladium dichloride (1.4 mg), trioctylmethylammonium
chloride (trade name: Aliquat 336, manufactured by Aldrich) (0.25 g) and toluene (40
ml) were blended and heated to 105°C. To the resultant reaction solution, a 2 M aqueous
sodium carbonate solution (6 ml) was added dropwise and refluxed for 20 hours. After
completion of the reaction, phenylboric acid (240 mg) was added and refluxed for further
4 hours. Subsequently, a 1.8 M aqueous sodium diethyldithiacarbamate solution (10
ml) was added and stirred at 80°C for 4 hours. The resultant reaction solution was
cooled to room temperature, then washed three times with water (30 ml), three times
with a 3 wt% aqueous acetic acid solution (30 ml) and three times with water (30 ml)
and purified by passing it through an alumina column and a silica gel column. The
resultant toluene solution was added dropwise to methanol (300 ml) and stirred for
one hour and thereafter, the resultant solid substance was filtrated and dried to
obtain polymer compound CP-3 (0.8 g) represented by the following formula:
wherein the numbers attached outside parentheses each represent a molar ratio of a
repeating unit.
[0291] The polystyrene-equivalent number average molecular weight of polymer compound CP-3
was 5.3 x 10
4 and the polystyrene-equivalent weight average molecular weight thereof was 1.9 x
10
5.
<Synthesis Example 10> (Synthesis of polymer compound P-8)
[0292] Under an inert gas atmosphere, compound MM-8 (7.28 g) represented by the following
formula MM-8:
2,7-dibromo-9,9-dioctylfluorene (4.94 g), compound MM-9(0.74 g), represented by the
following formula MM-9:
bis triphenylphosphine palladium dichloride (7.0 mg), trioctylmethylammonium chloride
(trade name: Aliquat 336, manufactured by Aldrich) (1.30 g) and toluene (100 ml) were
blended and heated to 105°C. To the resultant reaction solution, a 2 M aqueous sodium
carbonate solution (27 ml) was added dropwise and refluxed for 2 hours. After completion
of the reaction, phenylboric acid (120 mg) was added and refluxed for further 4 hours.
Subsequently, a 1.8 M aqueous sodium diethyldithiacarbamate solution (60 ml) was added
and stirred at 80°C for 4 hours. The resultant reaction solution was cooled to room
temperature, then washed three times with water (130 ml), three times with a 3 wt%
aqueous acetic acid solution (130 ml) and three times with water (130 ml) and purified
by passing it through an alumina column and a silica gel column. The resultant toluene
solution was added dropwise to methanol (1.5 L) and stirred for one hour. Thereafter,
the resultant solid substance was filtrated and dried to obtain polymer compound P-8
(8.0 g) represented by the following formula:
wherein the numbers attached outside parentheses each represent a molar ratio of a
repeating unit.
[0293] The polystyrene-equivalent number average molecular weight of polymer compound P-8
was 5.1 × 10
4 and the polystyrene-equivalent weight average molecular weight thereof was 1.4 ×
10
5.
[0294] Note that compound MM-8 represented by the above formula MM-8 was synthesized by
a method described in
WO200811165.
[0295] Furthermore, compound MM-9 represented by the above formula MM-9 was synthesized
by a method described in
EP1394188.
<Preparation of liquid composition>
[0296] Compound M-7, polymer compounds P-1 to P-7 and polymer compounds CP-1 to CP-3 were
each dissolved in xylene. In this manner, a liquid composition containing about 1
wt% of each of the compounds was prepared.
<Evaluation of residual film rate on glass substrate>
[0297] The liquid composition was added dropwise onto a glass substrate by a spin coater
(trade name: MS-A100 type, manufactured by Misawa) in the condition of 1000 rpm for
15 seconds. The film thickness (H
1) of the resultant film was measured by a profiler (trade name: P-16 +, manufactured
by KLA-Tencor Corporation).
[0298] Subsequently, in a globe box purged with nitrogen, the film on the glass substrate
was baked by use of a high power hot plate (trade name: HP-ISA, manufactured by AS
ONE Corporation), at a baking temperature shown in Table 1 for 20 minutes. The resultant
film on the glass substrate was cooled to room temperature, then soaked in a xylene
solution and then rinsed by a spin coater (trade name: MS-A100 type, manufactured
by Misawa) in the conditions of 1000 rpm for 15 seconds. The film thickness (H
2) of the film produced was measured by the profiler (trade name: P-16+, manufactured
by KLA-Tencor Corporation).
[0299] A value of (H
2)/(H
1) was defined as a residual film rate and the results obtained are shown in Table
1.
[Table 1]
|
Compound |
Residual film rate |
130°C Bake |
150°C Bake |
170°C Bake |
190°C Bake |
Example 13 |
M-7 |
44% |
54% |
84% |
99% |
Example 14 |
P-1 |
96% |
96% |
99% |
99% |
Example 15 |
P-2 |
74% |
88% |
92% |
96% |
Example 16 |
P-3 |
83% |
85% |
96% |
97% |
Example 17 |
P-4 |
22% |
38% |
52% |
74% |
Example 18 |
P-5 |
59% |
68% |
82% |
89% |
Example 19 |
P-6 |
74% |
90% |
98% |
99% |
Example 20 |
P-7 |
63% |
87% |
91% |
99% |
Comparative Example 4 |
CP-1 |
0% |
0% |
0% |
10% |
Comparative Example 5 |
CP-2 |
0% |
0% |
0% |
53% |
Comparative Example 6 |
CP-3 |
0% |
0% |
38% |
51% |
<Evaluation>
[0300] Compound M-7 and polymer compounds P-1 to P-7 were each confirmed to have high harden
ability compared to polymer compounds CP-1 to CP-3. Furthermore, even in the range
as low as 130°C to 150°C compared to 190°C, compound M-7 and polymer compounds P-1
to P-7 exhibited harden ability.
<Production and evaluation of electroluminescence (EL) device>
<Example 21>
Preparation of polymer compound <P-5> solution
[0301] The polymer compound <P-5> obtained above was dissolved in xylene to prepare a xylene
solution having a polymer concentration of 1.2 wt%.
Preparation of polymer compound <P-8> solution
[0302] The polymer compound <P-8> obtained above was dissolved in xylene to prepare a xylene
solution having a polymer concentration of 1.2 wt%.
Production ofEL device
[0303] On a glass substrate to which an ITO film of 150 nm in thickness was attached by
a sputtering method, a suspension solution of poly(3,4)ethylenedioxythiophenelpolystyrene
sulfonate (Baytron P AI4083 manufactured by Bayer) previously filtrated by a 0.2 µm
membrane filter, was applied by spin coating to form a film of 70 nm in thickness
and dried on a hot plate at 200°C for 10 minutes. Subsequently, using a xylene solution
of the polymer compound <P-5> obtained above, a film was formed by spin coating at
a rotation rate of 1600 rpm and heated on a hot plate at 150°C for 20 minutes to harden
the film. After completion of film formation, the thickness of the film was about
20 nm. Furthermore, using a xylene solution of the polymer compound <P-8> obtained
above, a film was formed by spin coating at a rotation rate of 1500 rpm. After the
film formation, the thickness of the film was about 60 nm. Furthermore, this was dried
under reduced pressure at 130°C for 10 minutes, and thereafter barium was vapor-deposited
as a cathode in a thickness of about 5 nm, and then aluminum was vapor-deposited in
a thickness of about 100 nm to produce an EL device. Note that vapor deposition of
a metal was initiated after a degree of vacuum reached 1 × 10
-4 Pa or less.
Performance of EL device
[0304] When voltage was applied to the resultant device, EL emission having a peak at 460
nm was provided from the device.
[0305] The time (life) for reducing a degree of brightness from the initial brightness (100
cd/m
2) to a half (50%) was as long as 26 hours.
<Example 22>
Preparation of polymer compound <P-6> solution
[0306] The polymer compound <P-6> obtained above was dissolved in xylene to prepare a xylene
solution having a polymer concentration of 1.2 wt%.
Preparation of polymer compound <P-8> solution
[0307] The polymer compound <P-8> obtained above was dissolved in xylene to prepare a xylene
solution having a polymer concentration of 1.2 wt%.
Production ofEL device
[0308] On a glass substrate to which an ITO film of 150 nm in thickness was attached by
a sputtering method, a suspension solution of poly(3,4)ethylenedioxythiophene/polystyrene
sulfonate (Baytron P AI4083 manufactured by Bayer) previously filtrated by a 0.2 µm
membrane filter, was applied by spin coating to form a film of 70 nm in thickness
and dried on a hot plate at 200°C for 10 minutes. Subsequently, using a xylene solution
of the polymer compound <P-6> obtained above, a film was formed by spin coating at
a rotation rate of 1600 rpm and heated on a hot plate at 150°C for 20 minutes to harden
the film. After the film formation, the thickness of the film was about 20 nm. Furthermore,
using a xylene solution of the polymer compound <P-8> obtained above, a film was formed
by spin coating at a rotation rate of 1500 rpm. After completion of film formation,
the thickness of the film was about 60 nm. Furthermore, this was dried under reduced
pressure at 130°C for 10 minutes, and thereafter barium was vapor-deposited as a cathode
in a thickness of about 5 nm, and then aluminum was vapor-deposited in a thickness
of about 100 nm to produce an EL device. Note that vapor deposition of a metal was
initiated after a degree of vacuum reached 1 × 10
-4 Pa or less.
Performance of EL device
[0309] When voltage was applied to the resultant device, EL emission having a peak at 470
nm was provided from the device.
[0310] The time (life) for reducing a degree of brightness from the initial brightness (100
cd/m
2) to a half (50%) was as long as 22 hours.
<Comparative Example 7>
Preparation of polymer compound <CP-1> solution
[0311] The polymer compound <CP-1> obtained above was dissolved in xylene to prepare a xylene
solution having a polymer concentration of 1.2 wt%.
Production of EL device
[0312] On a glass substrate to which an ITO film of 150 nm in thickness was attached by
a sputtering method, a suspension solution of poly(3,4)ethylenedioxythiophene/polystyrene
sulfonate (Baytron P AI4083 manufactured by Bayer) previously filtrated by a 0.2 µm
membrane filter was applied by spin coating to form a film of 70 nm in thickness and
dried on a hot plate at 200°C for 10 minutes. Subsequently, using a xylene solution
of the polymer compound <CP-1> obtained above, a film was formed by spin coating at
a rotation rate of 1600 rpm and heated on a hot plate at 150°C for 20 minutes to harden
the film. After completion of film formation, the thickness of the film was about
20 nm. Furthermore, using a xylene solution of the polymer compound <P-8> obtained
above, a film was formed by spin coating at a rotation rate of 1500 rpm. After the
film formation, the thickness of the film was about 60 nm. Furthermore, this was dried
under reduced pressure at 130°C for 10 minutes, and thereafter barium was vapor-deposited
as a cathode in a thickness of about 5 nm, and then aluminum was vapor-deposited in
a thickness of about 100 nm to produce an EL device. Note that vapor deposition of
a metal was initiated after a degree of vacuum reached 1 × 10
-4 Pa or less.
Performance of EL device
[0313] When voltage was applied to the resultant device, EL emission having a peak at 460
nm was provided from the device.
[0314] The time (life) for reducing a degree of brightness from the initial brightness (100
cd/m
2) to a half (50%) was one hour.
<Comparative Example 8>
Preparation of polymer compound <CP-2> solution
[0315] The polymer compound <CP-2> obtained above was dissolved in xylene to prepare a xylene
solution having a polymer concentration of 1.2 wt%.
Production of EL device
[0316] On a glass substrate to which an ITO film of 150 nm in thickness was attached by
a sputtering method, a suspension solution of poly(3,4)ethylenedioxythiophene/polystyrene
sulfonate (Baytron PAI4083 manufactured by Bayer) previously filtrated by a 0.2 µm
membrane filter was applied by spin coating to form a film of 70 nm in thickness and
dried on a hot plate at 200°C for 10 minutes. Subsequently, using a xylene solution
of the polymer compound <CP-2> obtained above, a film was formed by spin coating at
a rotation rate of 1600 rpm and heated on a hot plate at 150°C for 20 minutes to harden
the film. After completion of film formation, the thickness of the film was about
20 nm. Furthermore, using a xylene solution of the polymer compound <P-8> obtained
above, a film was formed by spin coating at a rotation rate of 1500 rpm. After the
film formation, the thickness of the film was about 60 nm. Furthermore, this was dried
under reduced pressure at 130°C for 10 minutes, and thereafter barium was vapor-deposited
as a cathode in a thickness of about 5 nm, and then aluminum was vapor-deposited in
a thickness of about 100 nm to produce an EL device. Note that vapor deposition of
a metal was initiated after a degree of vacuum reached 1 × 10
-4 Pa or less.
Performance of EL device
[0317] When voltage was applied to the resultant device, EL emission having a peak at 460
nm was provided from the device.
[0318] The time (life) for reducing a degree of brightness from the initial brightness (100
cd/m
2) to a half (50%) was 14 hours.
<Comparative Example 9>
Preparation of polymer compound <CP-3> solution
[0319] The polymer compound <CP-3> obtained above was dissolved in xylene to prepare a xylene
solution having a polymer concentration of 1.2 wt%.
Production of EL device
[0320] On a glass substrate to which an ITO film of 150 nm in thickness was attached by
a sputtering method, a suspension solution of poly(3,4)ethylenedioxythiophene/polystyrene
sulfonate (Baytron P AI4083 manufactured by Bayer) filtrated by a 0.2 µm membrane
filter was applied by spin coating to form a film of 70 nm in thickness and dried
on a hot plate at 200°C for 10 minutes. Subsequently, using a xylene solution of the
polymer compound <CP-3> obtained above, a film was formed by spin coating at a rotation
rate of 1600 rpm and heated on a hot plate at 150°C for 20 minutes to harden the film.
After completion of film formation, the thickness of the film was about 20 nm. Furthermore,
using a xylene solution of the polymer compound <P-8> obtained above, a film was formed
by spin coating at a rotation rate of 1500 rpm. After completion of film formation,
the thickness of the film was about 60 nm. Furthermore, this was dried under reduced
pressure at 130°C for 10 minutes, and thereafter barium was vapor-deposited as a cathode
in a thickness of about 5 nm, and then aluminum was vapor-deposited in a thickness
of about 100 nm to produce an EL device. Note that vapor deposition of a metal was
initiated after a degree of vacuum reached 1 × 10
-4 Pa or less.
Performance ofEL device
[0321] When voltage was applied to the resultant device, EL emission having a peak at 460
nm was provided from the device.
[0322] The time (life) for reducing a degree of brightness from the initial brightness (100
cd/m
2) to a half (50%) was 11 hours.
Industrial Applicability
[0323] A compound containing a 1,3-diene structure of the present invention can be used
as a material and the like for use in an organic layer of a light-emitting device.